Quantum dots (QDs) characterized by high absorption coefficients and elevated photoluminescence quantum yields have facilitated the development of micro-light-emitting diodes (Micro-LEDs) employing QD-based color conversion techniques. This methodology has shown considerable potential for the realization of full-color near-eye microdisplay devices. However, significant challenges persist, notably the pronounced leakage of blue light and the limited operational stability of these systems. In this study, we present the fabrication of perovskite quantum dot (PQD) patterns exhibiting high light conversion efficiency (LCE) and enhanced photostability by the incorporation of cascade curing within the direct in situ photolithography process. The pattern was generated through a thiol-ene click reaction initiated by UV exposure, followed by the formation of PQDs during the development stage, subsequent thermal cross-linking of the epoxy-amine system during postbaking further enhanced the stability of the PQDs. Using direct in situ cascade photolithography, colorful PQD patterns with a resolution of 10 μm, excellent fluorescence uniformity, and robust stability are successfully demonstrated. Furthermore, our findings suggest that the in situ cascade photolithography technique facilitates the generation of an increased number of nuclei from the perovskite precursor, thereby yielding a higher concentration of PQDs. This enhancement results in an impressive 99% absorption of blue light and an exceptionally high LCE of 38% within a 3.9 μm-thick film. Additionally, the PQDs maintain over 80% of their initial LCE after prolonged exposure of 100 h to continuous blue light irradiation at an intensity of 11 mW/cm2. This approach represents a significant advancement in the domain of direct photolithography and holds considerable promise for its integration into diverse optoelectronic devices.
Room-temperature phosphorescence (RTP) in proteins is exceptionally rare due to efficient quenching of triplet excitons in aqueous and biological environments. Here, we report a general supramolecular strategy to engineer phosphorescent proteins by embedding organic phosphors within protein scaffolds via host–guest interactions, where the confined microenvironment suppresses nonradiative decay and stabilizes triplet states, enabling bright and long-lived phosphorescence in both the solid state and aqueous media. The stabilized triplet excitons further endow these phosphorescent proteins with photocatalytic activity, allowing them to serve as efficient photosensitizers for photoinduced electron transfer-mediated reversible addition-fragmentation chain transfer polymerization in water, exhibiting excellent temporal control, predictable molecular weights, and narrow dispersities, with mechanistic studies supporting an electron-transfer pathway. Moreover, these systems enable polymerization-induced self-assembly to generate vesicular structures that encapsulate the photoactive proteins while retaining persistent afterglow emission, thereby integrating cellular-like compartmentalization with intrinsic optical traceability. This work establishes a versatile supramolecular route to RTP proteins and expands protein–phosphor assemblies toward artificial phosphorescent cells and light-driven biochemical systems.
Quantum dots (QDs) are essential for next-generation displays, yet their hydrophobic ligands cause poor adhesion to the substrates, thus leading to film detachment during photolithography. To address this, a carboxyl-functionalized phenol-formaldehyde (PF) oligomer was rationally designed and synthesized, in which each structural unit bears a carboxyl group to enable strong interfacial interactions with QD surfaces and underlying substrates, serving as a versatile platform for multifunctional photoresist development. Building on this, cinnamate (CA) groups were further introduced as photoactive crosslinking units and chain-end groups by polycondensation of the PF oligomer with phenylphosphonic dichloride, yielding the multifunctional PFP-CAs. The obtained PFP-CAs with multicarboxylate groups exhibit high viscosity and excellent solubility in the solvent of propylene glycol methyl ether acetate (PGMEA). A QD photoresist (QDPR) formulation was subsequently prepared by dispersing QDs with PFP-CAs in PGMEA, and high-resolution patterns with a feature size down to 5 mu m has been achieved, demonstrating that the multicarboxylate architecture effectively overcomes the adhesion limitations of conventional QDPRs. These findings establish PFP-CAs as a promising resin platform for high-resolution QD photolithography, offering a practical and scalable pathway toward the precise color-patterning required in next-generation manufacturing.
Triggering near-infrared (NIR) room-temperature phosphorescence (RTP) poses a major challenge, because the narrow optical gap promotes nonradiative decay via thermal vibrations. Here, we report a series of high-performance RTP materials based on graphene nanoribbons, namely nHBT (n = 1-4). Unlike the modulation of fluorescence by extending π-conjugation, enhancing molecular conjugation more effectively induces red-shifted phosphorescence, enabling NIR emission. By doping nHBT in polyvinylpyrrolidone, NIR RTP with a maximum emission wavelength of 898 nm is achieved, exhibiting a quantum yield of 2.9% and a lifetime of 1.9 ms. Moreover, the rigid fused-ring framework suppresses molecular motions and nonradiative decay, resulting in a persistent afterglow even at 377 K. Well-dispersed NIR RTP nanoparticles were further obtained using polystyrene-b-poly(ethylene glycol) as the host and surfactant. In vivo studies demonstrate excellent capability to suppress background fluorescence, achieving a signal-to-background ratio as high as 47.3 ± 4.2. These results highlight rigid graphene nanoribbons as a versatile platform for high-performance NIR RTP and biophotonic applications.
Seven spirooxazine derivatives (M1–M7) with potential pharmacological activity were synthesized through a metal-free multicomponent spirocyclization of alkyne, isatin, and quinoline. The obtained spirooxazines have typical aggregation-caused quenching characteristic. M3 only showed a real-time and high-selective fluorescent enhancement response to human serum albumin (HSA), while there was almost no response to bovine serum albumin and other proteins. Experiments and simulations have shown that M3 enters the hydrophobic cavity of HSA and forms various noncovalent interactions with amino acid residues, resulting to restricts the intramolecular motion and enhances fluorescence emission of M3. In addition, M3 has the same emission intensity in pure solution, simulated serum, and real human serum at the same HSA concentration, indicating its excellent anti-interference ability and advantages in accuracy and convenience. These results show that spirooxazine provides an effective scaffold for selective HSA recognition and offers a useful strategy for the discrimination of highly homologous proteins.
Open-shell organic radical emitters hold promise for improving exciton utilization efficiency; however, triggering stable organic radical emission is rarely documented due to its high chemical reactivity. Herein, we present a universal design strategy for organic radical emitters by using an excited triplet state as an intermediate. The system features a long-lived roomtemperature phosphorescence (RTP) guest embedded within a host matrix. Systematic investigations reveal a dynamic conversion from orange RTP to red radical complex emission under continuous photoexcitation. This phenomenon arises from long-lived triplet excitons, which facilitate photoinduced charge transfer (PICT) from the host to the guest, thereby triggering efficient radical emission with long-term chemical stability. We further demonstrate the excellent reversibility between guest RTP and host radical emission through alternating heat/recrystallization and photoexcitation processes. This triplet-mediated PICT strategy provides a promising pathway for the development of radical emitters with high efficiency towards advanced electroluminescent devices.
Pyrrole is one of the most common five-membered heterocycles, and its units can be found in many natural products (such as chlorophyll and vitamin B12) and biologically active drugs (e.g., atorvastatin and calcimycin). Owing to their electron-rich properties and multiple modifiable sites, pyrrole derivatives have been widely developed and used in various fields, including medicine and optoelectronic materials. For more than 10 years, we have been working on the development of multi-aryl pyrroles (MAPs) considering the characteristics of aggregation-induced emission (AIE) for biological diagnostic applications. Herein, the structural design of MAPs and their corresponding AIE properties were briefly introduced. Then, MAPs that emit across the full spectrum from ultraviolet-visible to near-infrared II wavelengths were summarized for their application in analyzing and detecting biological substances, bioimaging, and phototherapy. Finally, we demonstrate the potential of MAPs in advancing biomedicine, clinical diagnosis, and cancer treatment.
Near-infrared room-temperature phosphorescent (NIR-RTP) materials feature the advantages of large Stokes shift, long emission lifetime, and high penetration ability, and have been broadly applied in bio-medical imaging, fiber optic telecommunication, and night vision-readable display. Developing organic NIR-RTP materials heavily relies on the long-conjugated chemical structures. The large conjugation could result in aggregation caused quenching, complex synthesis, poor processability, and high biological toxicity. Herein, by solution blending poly(iminofuran-spiro-pyrrolone) (PISP) with polystyrene (PS), we construct a nonconventional NIR-RTP polymer alloy without significantly extensive conjugation. The PISP was synthesized via a catalyst-free multicomponent polymerization in air with high molecular weights (up to 41000 g/mol) and decent yields (up to 84%). Although lacking classical luminescent segments and largely extended conjugation, PISPs exhibit the clusterization-triggered cryogenic phosphorescence. More importantly, upon solution blending PISP with PS, the resultant polymer alloy shows a NIR-RTP emission up to 715 nm with a Stokes shift of 375 nm. This work will be of interest for developing luminescent materials for the optoelectronic devices, in vivo imaging, and flexible electronics.
H3N2 influenza virus poses a persistent serious threat to human health every year. Currently available detection methods often involve multi-step complex procedures. Such as enzyme-linked immunosorbent assay (ELISA) requires centrifugation, incubation with multiple antibodies, and addition of enzyme-labeled reagents. Reverse transcription-polymerase chain reaction (RT-PCR) necessitates RNA extraction, reverse transcription, and thermal cycling for amplification. These time-consuming and labor-intensive protocols hinder timely response. In this work, fluorescein (FLC), 5-carboxyfluorescein (5-FAM) and fluorescein-5-thiosemicarbazide (5-FTSC) exhibited almost no fluorescence emission in pure DMSO and strong fluorescence emission in DMSO/H2O with high water fraction. Based on this property, we presented a separation-free, rapid, and quantitative detection method using three compounds as "turn-on" fluorescent probes to detect H3 and N2 spike proteins in mixed solutions. Among them, the limit of detection of FLC probe to N2 was as low as 0.442 nmol/L. Simulations based on molecular docking indicated that the fluorescent probe was able to enter the hydrophobic cavity of the protein restricted by the surrounding amino acid residues, and that the intramolecular motion was reduced to achieve a fluorescence enhanced response. Finally, comparative experiments using real H3N2 virus samples showed that the fluorescence probe method not only achieved faster and more cost-effective detection than ELISA, but also produced more consistent results, indicating the higher reliability of detection results. The separation-free detection method will provide a valuable tool for early public health monitoring.
This review highlights the innovative design principles and applications of low- T g polymer-based flexible RTP materials, paving the way for next-generation soft optoelectronics.
The development of pure organic photosensitizers remains challenging due to the low intersystem crossing efficiency and the instability of triplet excitons. Herein, fused-ring phosphorescent molecules enhance visible-light absorption, with heteroatom-rich structures breaking the restriction of low triplet excitons. A derivative, 2,3,5,6,9,10-hexabutoxy-8-phenyldithieno-tribenzo-pyridine (TPy), exhibits high ISC efficiency and efficiently sensitizes Fe-catalysts for CO2 photoreduction to CO. We further developed a self-assembly method to stabilize triplet excitons by embedding TPy within the rigid core of amphiphilic polymer nanoparticles. The hydrophobic core of the nanoparticles significantly prolongs the excited-state lifetime, while the hydrophilic shell ensures excellent dispersibility and stability. This system achieves a turnover number of 2041 and retains 93.5% of its initial activity after three cycles. Our work provides a general strategy for designing stable and highly efficient organic photosensitizers, paving the way for sustainable photoredox catalysis.
The detection of proteins is crucial in the fields of disease diagnosis and drug development. Detection of proteins by aggregation-induced emission (AIE) probes is a quick and convenient method. However, the current AIE probes for the specific protein detection mainly depended on experimental test, lacking a guiding strategy. This study presented a novel approach to design AIE probes for detecting protein using molecular docking depending on AIE luminescence mechanism of the restriction of intramolecular motions. As an example to show its feasibility, three AIE probes with pyrrolo[3,2-b]pyrrole motif were designed and synthesized. The binding of the three probes to nine common proteins were predicted in advance using the molecular docking technique, obtaining information including intermolecular forces, binding energy, and binding sites between probes with proteins. The prediction results were verified through experimental data, and the mutual comparation of experimental and molecular docking results confirmed the reliability of the information provided by the molecular docking technique. Furthermore, the probes TPPP-2Na and TPPP-4Na exhibited limit of detection as low as 0.33 μg/mL for BSA and 0.35 μg/mL for HSA, respectively. The study revealed an innovative approach for the screening and molecular design of AIE probes for the detection of proteins.
Organic near-infrared (NIR) room-temperature phosphorescent (RTP) materials hold great potential for bioimaging due to their ability to eliminate background noise and tissue autofluorescence. Here, we synthesized octa-ring fused RTP molecules (TPP-BN and TPP-BF) with B─N coordination bonds via a two-step reaction, enabling NIR phosphorescent emission at 819 nm and a 28.6 ms lifetime. Using PMMA-b-PEG as host and surfactant to stabilize the RTP molecules, we fabricated PMMA-b-PEG based nanoparticles (PNPs) with five-fold brighter afterglow than conventional F127-based methods (FNPs). We further developed a granzyme B (GrB)-responsive nanoprobe (Q-BFNP) that achieves specific and quantitative detection. In vivo studies demonstrated their ability to monitor and distinguish tumor immune response with the signal-to-background ratio (SBR) as high as 216.4. This study provides a new method for constructing NIR organic RTP probes and advances applications of RTP materials in real-time, high-contrast bioimaging and tumor immune monitoring.
Quantitative oxygen detection, especially at low concentrations, holds significant importance in the realms of biology, complex environments, and chemical process engineering. Due to the high sensitivity and rapid response of the triplet excitons of phosphorescence to oxygen, pure organic room-temperature phosphorescence (RTP) materials have garnered widespread attention in recent years for oxygen detection. However, simultaneously achieving ultralong phosphorescence at room temperature and quantitative oxygen detection from pure organic host-guest doped materials poses challenges. The densely packed materials may decrease non-radiative decay to increase the phosphorescence, but are unsuitable for oxygen diffusion in oxygen detection. Herein, the oxygen sensitivity of host-guest doped RTP materials using 4-bromo-N,N-bis(4-(tert- N , N-bis(4-( tert- butyl)phenyl)aniline (TPABuBr) as the host and 6-bromo-2-butyl-1H-benzo[de]isoquinoline-1,3(2H)-dione H-benzo[de]isoquinoline-1,3(2 H )-dione (NIBr) as the guest was developed. The doped material exhibits fluorescence-phosphorescence dual-emission behavior at room temperature. The tert-butyl groups in TPABuBr facilitate appropriate intermolecular spacing in the crystal state, enhancing oxygen permeability. Therefore, oxygen penetration can quench the phosphorescence emission. The observed linear relationship between the phosphorescence intensity of the doped material and the oxygen volume fraction conforms to the Stern-Volmer equation, suggesting its potential for quantitative analysis of oxygen concentration. The calculated limit of detection is 0.015% (phi), phi ), enabling the analysis of oxygen with a volume fraction of less than 2.5% (phi). phi ). Moreover, the doped materials demonstrate rapid response and excellent photostability, indicating their potential utility as oxygen sensors. This study elucidates the design and characteristics of NIBr/TPABuBr doped materials, highlighting their potential application in oxygen concentration detection and offering insights for the design of oxygen sensors.
As one of the high pathogenic influenza viruses, H1N1 virus easily induces to serious diseases, even leading to death. To date, all detection methods for H1N1 virus had shortcomings, including high equipment cost, time consumption, and etc. Therefore, a novel detection method should be established to achieve more convenient, rapid, and low-cost detection. In this work, an isomer of HPBmN-I with aggregation-induced emission characteristic was firstly synthesized on the basis of our previous reported HPBpN-I. The results showed that HPBmN-I only selectively binds to N1 in the presence of H1, while HPBpN-I can exhibit total fluorescence response to H1 and N1 in H1/N1 mixture. The limited of detection (LOD) of HPBmN-I to N1 was estimated to be 20.82 ng/mL in normal saline (NS) according to the IUPAC-based approach. The simulation calculations based on molecular docking revealed that four HPBmN-I molecules combine well with the hydrophobic cavity of N1 and achieve the fluorescence enhancement due to size matching with each other. The combination of HPBpN-I and HPBmN-I as probes was successfully used to quantitatively detect H1 and N1 in real H1N1 virus. Compared to enzyme-linked immunosorbent assay (ELISA) method, the established method not only showed the same detection accuracy but also had the advantages of real-time, ease of preparation, and low-cost, demonstrating potential market prospects.
Near-infrared circularly polarized organic room temperature phosphorescence is achieved by doping a naphthalimide derivative guest into a tartaric acid derivative host.
In this perspective, the progress in ion-regulated organic RTP materials and described the roles of ions, including ion–π interactions, electrostatic interactions, and coordinate interactions, have been summarized.
New strategies for the synthesis of stable organic luminescent radicals with their unique electronic structures are highly desirable. Herein, we designed and synthesized a novel arylboron compound BN-2Ph with radical-generating potential. BN-Ph was used as the guest molecule in the host-guest system, exhibiting high-efficiency and persistent phosphorescent emission. The long lifetime triplet exciton induced unexpected luminescent radicals with red emission in the doped crystalline state, which could be rapidly and reversibly generated by heating and recrystallizing. The quantitative electron paramagnetic resonance analysis and theoretical calculations suggest that the triplet-stabled photoinduced electron transfer mechanism between host and guest molecules is responsible for the generation and stabilization of radicals. This doped system was applied in AND and OR logic gates, showing its potential application in logic circuits. Our results provide a simple molecular-design strategy for achieving stable organic luminescent radicals.
Organic room-temperature phosphorescent (RTP) materials have garnered significant attention owing to their unique photophysical properties. Traditionally, the stabilization of triplet excitons in RTP materials necessitates a crystalline matrix or rigid polymer chain, which limits their use in flexible materials. In contrast, hydrogels offer biocompatibility, softness, and ease of processing. Therefore, incorporating phosphorescent molecules into hydrogel systems can expand the application potential of RTP materials. This concept summarizes recent advancements in RTP hydrogels, emphasizing their synthetic strategies and diverse applications.