Less is More: Asymmetric D-A Type Agent to Achieve Dynamic Self-Assembled Nanoaggregates for Long-Acting Photodynamic Therapy.

To enhance the phototheranostic performance, agents with high reactive oxygen species (ROS) generation, good tumor-targeting ability, and prolonged retention are urgently needed. However, symmetric donor-acceptor (D-A) type agents usually produce spherical nanoaggregates, leading to good tumor targeting but inferior retention. Rod-like nanoaggregates are desired to extend their retention in tumors; however, this remains a challenge. In particular, agents with dynamically changeable shapes that integrate merits of different morphologies are seldomly reported. Therefore, self-assembled organic nanoaggregates with smart shape tunability are designed here using an asymmetric D-A type TIBT. The photoluminescence quantum yield in solids is up to 52.24% for TIBT. TIBT also exhibits high ROS generation in corresponding nanoaggregates (TIBT-NCs). Moreover, dynamic self-assembly in shape changing from nanospheres to nanorods occurrs in TIBT-NCs, contributing to the enhancement of ROS quantum yield from 0.55 to 0.72. In addition, dynamic self-assembly can be observed for both in vitro and in vivo, conferring TIBT-NCs with strong tumor targeting and prolonged retention. Finally, efficient photodynamic therapy to inhibit tumor growth is achieved in TIBT-NCs, with an inhibition rate of 90%. This work demonstrates that asymmetric D-A type agents can play significant roles in forming self-assembled organic nanoaggregates, thus showing great potential in long-acting cancer therapy.

One Stone, Two Birds: High-Brightness Aggregation-Induced Emission Photosensitizers for Super-Resolution Imaging and Photodynamic Therapy.

Most aggregation-induced emission (AIE) luminogens exhibit high brightness, excellent photostability, and good biocompatibility, but these AIE-active agents, which kill two birds with one stone to result in applications in both stimulated emission depletion (STED) super-resolution imaging and photodynamic therapy (PDT), have not been reported yet but are urgently needed. To meet the requirements of STED nanoscopy and PDT, D-A-π-A-D type DTPABT-HP is designed by tuning conjugated π spacers. It exhibits red-shifted emission, high PLQY of 32.04%, and impressive 1O2 generation (9.24 fold compared to RB) in nanoparticles (NPs). Then, DTPABT-HP NPs are applied in cell imaging via STED nanoscopy, especially visualizing the dynamic changes of lysosomes in the PDT process at ultrahigh resolution. After that, in vivo PDT was also conducted by DTPABT-HP NPs, resulting in significantly inhibited tumor growth, with an inhibition rate of 86%. The work here is beneficial to the design of multifunctional agents and the deep understanding of their phototheranostic mechanism in biological research.

Recent advances of organic emitters in deep-red light-emitting electrochemical cells.

Light-emitting electrochemical cells (LECs) are kind of easily fabricated and low-cost light-emitting devices that can efficiently convert electric power to light energy. Compared with blue and green LECs, the performance of deep-red LECs is limited by the high non-radiative rate of emitters in long-wavelength region. While various organic emitters with deep-red emission have been developed to construct high-performance LECs, including polymers, metal complexes, and organic luminous molecules (OLMs), but this is seldom summarized. Therefore, we overview the recent advances of organic emitters with emission at the deep-red region for LECs, and specifically highlight the molecular design approach and electrochemiluminescence performance. We hope that this review can act as a reference for further research in designing high-performance deep-red LECs.

Aggregation-induced emission (AIE)-active metallacycles with near-infrared emission for photodynamic therapy.

Multifunctional metallacycles with solid-state emission are highly important in cancer therapy. Here, an aggregation-induced emission (AIE)-active metallacycle of DTPABT-MC-R is developed with efficient emission in the NIR region in the solid state (PLQYs = 4.92%). DTPABT-MC-R-based nanoparticles also display excellent photo-stability, and impressive photosensitive characteristics (ROS efficiency = 10.74%), finally leading to applications in cellular imaging and photodynamic therapy (PDT).

Aggregation-Induced Emission (AIE), Life and Health.

Light has profoundly impacted modern medicine and healthcare, with numerous luminescent agents and imaging techniques currently being used to assess health and treat diseases. As an emerging concept in luminescence, aggregation-induced emission (AIE) has shown great potential in biological applications due to its advantages in terms of brightness, biocompatibility, photostability, and positive correlation with concentration. This review provides a comprehensive summary of AIE luminogens applied in imaging of biological structure and dynamic physiological processes, disease diagnosis and treatment, and detection and monitoring of specific analytes, followed by representative works. Discussions on critical issues and perspectives on future directions are also included. This review aims to stimulate the interest of researchers from different fields, including chemistry, biology, materials science, medicine, etc., thus promoting the development of AIE in the fields of life and health.

A Feasible Strategy for a Highly Efficient Thermally Activated Delayed Fluorescence Emitter Over 900 nm Based on Phenalenone Derivatives.

Near-infrared (NIR) organic light-emitting diodes (OLEDs) suffer from the low external electroluminescence (EL) quantum efficiency (EQE), which is a critical obstacle for potential applications. Herein, 1-oxo-1-phenalene-2,3-dicarbonitrile (OPDC) is employed as an electron-withdrawing aromatic ring, and by incorporating with triphenylamine (TPA) and biphenylphenylamine (BBPA) donors, two novel NIR emitters with thermally activated delayed fluorescence (TADF) characteristics, namely OPDC-DTPA and OPDC-DBBPA, are first developed and compared in parallel. Intense NIR emission peaks at 962 and 1003 nm are observed in their pure films, respectively. Contributed by the local excited (LE) characteristics in the triplet (T1 ) state in synergy with the charge transfer (CT) characteristics for the singlet (S1 ) state to activate TADF emission, the solution processable doped NIR OLEDs based on OPDC-DTPA and OPDC-DBBPA yield EL peaks at 834 and 906 nm, accompanied with maximum EQEs of 0.457 and 0.103 %, respectively, representing the state-of-the-art EL performances in the TADF emitter-based NIR-OLEDs in the similar EL emission regions so far. This work manifests a simple and effective strategy for the development of NIR TADF emitters with long wavelength and efficiency synchronously.

Aggregation-Induced Emission by Molecular Design: A Route to High-Performance Light-Emitting Electrochemical Cells.

The emission efficiency of organic semiconductors (OSCs) often suffers from aggregation caused quenching (ACQ). An elegant solution is aggregation-induced emission (AIE), which constitutes the design of the OSC so that its morphology inhibits quenching π-π interactions and non-radiative motional deactivation. The light-emitting electrochemical cell (LEC) can be sustainably fabricated, but its function depends on motion of bulky ions in proximity of the OSC. It is therefore questionable whether the AIE morphology can be retained during LEC operation. Here, we synthesize two structurally similar OSCs, which are distinguished by that 1 features ACQ while 2 delivers AIE. Interestingly, we find that the AIE-LEC significantly outperforms the ACQ-LEC. We rationalize our finding by showing that the AIE morphology remains intact during LEC operation, and that it can feature appropriately sized free-volume voids for facile ion transport and suppressed non-radiative excitonic deactivation.

All-in-One Theranostic Platforms: Deep-Red AIE Nanocrystals to Target Dual-Organelles for Efficient Photodynamic Therapy.

Aggregation-induced emission (AIE) nanoparticles have been widely applied in photodynamic therapy (PDT) over the past few years. However, amorphous nanoaggregates usually occur in their preparation, resulting in loose packing with disordered molecular structures. This still allows free intramolecular motions, thus leading to limited brightness and PDT efficiency. Herein, we report deep-red AIE nanocrystals (NCs) of DTPA-BS-F by following the facile method of nanoprecipitation. It is observed that DTPA-BS-F NCs possess not only a high photoluminescence quantum yield value of 8% in the deep-red region (600-850 nm) but also an impressive reactive oxygen species (ROS) generation efficiency of up to 69%. Moreover, DTPA-BS-F NCs targeting dual-organelles of lysosomes and nucleus to generate ROS are also achieved, thus boosting the PDT effect in cancer therapy both in vitro and in vivo. This work provides high-performance AIE NCs to simultaneously target two organelles for efficient photodynamic therapy, indicating their promising application in all-in-one theranostic platforms.

Aggregation-Induced Emission (AIE) in Super-resolution Imaging: Cationic AIE Luminogens (AIEgens) for Tunable Organelle-Specific Imaging and Dynamic Tracking in Nanometer Scale.

Organelle-specific imaging and dynamic tracking in ultrahigh resolution is essential for understanding their functions in biological research, but this remains a challenge. Therefore, a facile strategy by utilizing anion-π+ interactions is proposed here to construct an aggregation-induced emission luminogen (AIEgen) of DTPAP-P, not only restricting the intramolecular motions but also blocking their strong π-π interactions. DTPAP-P exhibits a high photoluminescence quantum yield (PLQY) of 35.04% in solids, favorable photostability and biocompatibility, indicating its potential application in super-resolution imaging (SRI) via stimulated emission depletion (STED) nanoscopy. It is also observed that this cationic DTPAP-P can specifically target to mitochondria or nucleus dependent on the cell status, resulting in tunable organelle-specific imaging in nanometer scale. In live cells, mitochondria-specific imaging and their dynamic monitoring (fission and fusion) can be obtained in ultrahigh resolution with a full-width-at-half-maximum (fwhm) value of only 165 nm by STED nanoscopy. This is about one-sixth of the fwhm value in confocal microscopy (1028 nm). However, a migration process occurs for fixed cells from mitochondria to nucleus under light activation (405 nm), leading to nucleus-targeted super-resolution imaging (fwhm= 184 nm). These findings indicate that tunable organelle-specific imaging and dynamic tracking by a single AIEgen at a superior resolution can be achieved in our case here via STED nanoscopy, thus providing an efficient method to further understand organelle's functions and roles in biological research.

Facilely prepared aggregation-induced emission (AIE) nanocrystals with deep-red emission for super-resolution imaging.

Organic nanocrystals (NCs) with high brightness are highly desirable for biological imaging. However, the preparation of NCs by a facile and fast method is still challenging. Herein, an aggregation-induced emission (AIE) luminogen of 4,4'-(5,6-difluorobenzo[c][1,2,5]thiadiazole-4,7-diyl)bis(N,N-bis(4-methoxyphenyl)aniline) (DTPA-BT-F) in the deep-red region is designed with intensive crystalline features to obtain NCs by kinetically controlled nanoprecipitation. The prepared AIE NCs with high brightness and good photo-stability are then applied in super-resolution imaging via stimulated emission depletion (STED) nanoscopy. As observed, the nanostructures in lysosomes of both fixed and live cells are well visualized with superior lateral resolutions under STED nanoscopy (full width at half maximum values, 107 and 108 nm) in contrast to that in confocal imaging (548 and 740 nm). More importantly, dynamic monitoring and long-term tracking of lysosomal movements in live HeLa cells, such as lysosomal contact, can also be carried out by using DTPA-BT-F NCs at a superior resolution. To the best of our knowledge, this is the first case of AIE NCs prepared by nanoprecipitation for STED nanoscopy, thus providing a new strategy to develop high performance imaging agents for super-resolution imaging.

Recent Advances on Organic Fluorescent Probes for Stimulated Emission Depletion (STED) Microscopy.

Stimulated emission depletion (STED) microscopy has become a useful tool for visualization and dynamic monitoring at an ultra-high resolution in biological research and material science. For STED technology, fluorescent probes are irreplaceable in the imaging process. Among these probes, organic fluorescent probes have superior photo-stability, high brightness, large Stokes' shifts and excellent biocompatibility, thus are widely applied in STED microscopy. Based on this consideration, this review presents the recent advances on organic fluorescent probes for STED microscopy, including typical organic fluorescent probes, aggregation-induced emission luminogens (AIEgens), polymer dots, and other nanoparticles. The applications of organic fluorescent probes in biological imaging, such as in live-cell, live-tissue, and in vivo imaging, as well as in material monitoring at the nanoscale using STED microscopy, are also included. This review provides the guidelines for the design of new materials that can be used to enhance the imaging performance of STED microscopy, thus leading to real-world applications.

Recent advances in luminescent materials for super-resolution imaging via stimulated emission depletion nanoscopy.

Stimulated emission depletion (STED) nanoscopy is a promising fluorescence microscopy to detect unresolvable structures at the nanoscale level and then achieve a superior imaging resolution in materials science and biological research. However, in addition to the optimization of the microscope, luminescent materials in STED nanoscopy are also of great significance to obtain imaging, visualization and even long-term tracking at an ultra-high resolution (less than 100 nm), but this is seldom summarized. Based on this consideration, recent progress on STED fluorophores for super-resolution imaging is outlined here, including inorganic fluorophores, fluorescent proteins, organic luminescent materials, aggregation-induced emission (AIE) luminogens, and fluorescent nanoparticles. Characteristics of these aforementioned STED fluorophores are also included and compared to provide a deep understanding of the relationship between the properties in luminescent materials and their performance in STED imaging. According to the results on such luminescent materials, it is anticipated that guidelines to select proper probes and even develop new materials for super-resolution imaging via STED nanoscopy will be provided here, finally promoting the development of super-resolution imaging in both materials science and biological research.

Versatile Nanoplatforms with enhanced Photodynamic Therapy: Designs and Applications.

As an emerging antitumor strategy, photodynamic therapy (PDT) has attracted intensive attention for the treatment of various malignant tumors owing to its noninvasive nature and high spatial selectivity in recent years. However, the therapeutic effect is unsatisfactory on some occasions due to the presence of some unfavorable factors including nonspecific accumulation of PS towards malignant tissues, the lack of endogenous oxygen in tumors, as well as the limited light penetration depth, further hampering practical application. To circumvent these limitations and improve real utilization efficiency, various enhanced strategies have been developed and explored during the past years. In this review, we give an overview of the state-of-the-art advances progress on versatile nanoplatforms for enhanced PDT considering the enhancement from targeting or responsive, chemical and physical effect. Specifically, these effects mainly include organelle-targeting function, tumor microenvironment responsive release photosensitizers (PS), self-sufficient O2 (affinity oxygen and generating oxygen), photocatalytic water splitting, X-rays light stimulate, surface plasmon resonance enhancement, and the improvement by resonance energy transfer. When utilizing these strategies to improve the therapeutic effect, the advantages and limitations are addressed. Finally, the challenges and prospective will be discussed and demonstrated for the future development of advanced PDT with enhanced efficacy.

Continuous phase regulation of MoSe2 from 2H to 1T for the optimization of peroxidase-like catalysis.

Nanozymes are a new generation of artificial enzymes that address the limitations of natural enzymes, with numerous reports on the development of high performance nanozymes for various applications. Herein, the phase regulation of network-like MoSe2 from the metal 1T phase to semiconductor 2H phase was achieved under different reaction conditions by a facile but efficient microwave-assisted solvothermal method. The coexisting 1T/2H-MoSe2 with edge enriched and defective nanostructures showed great enhancement of the peroxidase-like properties. This high enzymatic activity may arise from optimized active sites of 1T/2H-MoSe2, effectively leading to a rapid charge transfer within the substrate. In addition, chitosan functionalization not only greatly improves the dispersion stability of MoSe2, but also significantly increases its peroxidase-like activity, probably due to its enhanced affinity to hydrogen peroxide (H2O2). Based on these results we have established a highly sensitive colorimetric assay for the detection of H2O2 and glucose in human serum.

Tuning molecular aggregation to achieve highly bright AIE dots for NIR-II fluorescence imaging and NIR-I photoacoustic imaging.

Currently, bright aggregation-induced emission luminogens (AIEgens) with high photoluminescence quantum yields (PLQYs) in the NIR-II region are still limited, and thus an efficient strategy to enhance NIR-II fluorescence performance through tuning molecular aggregation is proposed here. The synthesized donor-acceptor tailored AIEgen (DTPA-TBZ) not only exhibits an excellent absorptivity in the NIR-I region, but also good fluorescence signals in the NIR-II region with an emission extending to 1200 nm. Benefiting from such improved intramolecular restriction and aggregation, a significant absolute PLQY value of 8.98% was obtained in solid DTPA-TBZ. Encouragingly, the resulting AIE dots also exhibit a high relative PLQY of up to 11.1% with IR 26 as the reference (PLQY = 0.5%). Finally, the AIE dots were applied in high performance NIR-II fluorescence imaging and NIR-I photoacoustic (PA) imaging: visualization of abdominal vessels, hind limb vasculature, and cerebral vessels with high signal to background ratios was performed via NIR-II imaging; Moreover, PA imaging has also been performed to clearly observe tumors in vivo. These results demonstrate that by finely tuning molecular aggregation in DTPA-TBZ, a good NIR-I absorptivity and a highly emissive fluorescence in the NIR-II region can be achieved simultaneously, finally resulting in a promising dual-modal imaging platform for real-world applications to achieve precise cancer diagnostics.

A Facilely Synthesized Dual-State Emission Platform for Picric Acid Detection and Latent Fingerprint Visualization.

To achieve a highly efficient, dual-state emission platform for picric acid (PA) detection and latent fingerprint (LFP) visualization, flexible alkyl chains have been facilely attached to the commercial organic dye 3,4,9,10-perylenetetracarboxylic dianhydride to provide the target perylenetetracarboxylate molecules PTCA-C4, PTCA-C6, and PTCA-C12. Interestingly, all these molecules exhibited impressive fluorescence characteristics with high photoluminescence quantum yields (PLQYs) of around 93.0 % in dilute solution. Also, emissive features were observed in the solid state because close molecular packing is prevented by the alkyl chains, especially for PTCA-C6, which has a high PLQY value of 49.0 %. Benefiting from its impressive fluorescence performance in both solution and as aggregates, PTCA-C6 was used as a dual-state emission platform for PA detection and also LFP visualization. For example, double-responsive fluorescence quenching in solution was observed in PA detection studies, resulting in high quenching constants (KSV ) and also low limit-of-detection values. Furthermore, the fingerprint powder based on PTCA-C6 also presented an impressive performance on various substrates in terms of fluorescence intensity and resolution, clearly providing the specific fine details of latent fingerprints. These results demonstrate that the facilely synthesized PTCA-C6 with efficient dual-state emission exhibits great potential in the real-world applications of PA detection and LFP visualization.

Deep-Red Fluorescent Organic Nanoparticles with High Brightness and Photostability for Super-Resolution in Vitro and in Vivo Imaging Using STED Nanoscopy.

To achieve super-resolution imaging in biological research using stimulated emission depletion (STED) nanoscopy, organic luminescent materials and their corresponding fluorescent nanoparticles with high brightness and photostability are of great significance. Herein, donor-acceptor-typed DBTBT-4C8 bearing flexible alkyl chains was developed, not only to afford deep-red emission from 600 to 800 nm but also to obtain high fluorescent brightness with the absolute photoluminescence quantum yields of 25%. After that, well-defined and monodispersed spherical nanoparticles using DBTBT-4C8 with bright emission, excellent biocompatibility, and photostability, which can easily mix with amphipathic block polymers, were then produced for super-resolution in vitro and in vivo imaging using STED nanoscopy. The observations showed that in contrast to confocal microscopy with a full width at half-maximum (FWHM) value of ≈400 nm, superior resolution with a significantly improved FWHM value of only 100 nm was achieved in biomedical cell imaging, which was also used to reconstruct three-dimensional images of stained HeLa cells at an ultrahigh resolution. More importantly, by using the prepared fluorescent organic nanoparticles (FONPs) in STED nanoscopy, in vivo imaging in glass catfish with largely enhanced resolution was also successfully achieved, demonstrating that these developed deep-red FONPs here are highly suitable for super-resolution in vitro and in vivo imaging using STED nanoscopy.

Super-Resolution Visualization of Self-Assembling Helical Fibers Using Aggregation-Induced Emission Luminogens in Stimulated Emission Depletion Nanoscopy.

Organic fluorophores for stimulated emission depletion (STED) nanoscopy usually suffer from quenched emission in the aggregate state and inferior photostability, which largely limit their application in real-time, in situ, and long-term imaging at an ultrahigh resolution. Herein, an aggregation-induced emission (AIE) luminogen of DP-TBT with bright emission in solid state (photoluminescence quantum yields = 25%) and excellent photostability was designed to meet the requirements in STED nanoscopy. In addition to its excellent fluorescence properties, DP-TBT could also easily form self-assembling helixes and finally be well-visualized by super-resolution STED nanoscopy. The observations showed that helical fibers of DP-TBT as dashed lines had a much decreased fiber width with also a full width at half-maximum value of only 178 nm, which is ∼6 times higher than solid lines obtained by confocal microscopy (1154 nm). The STED nanoscopic data were also used to reconstruct 3D images of assembled helixes. Finally, by long-term tracking and dynamic monitoring, the formation and growth of helical fibers by DP-TBT in self-assembly processes were successfully obtained. These findings imply that highly emissive AIEgens with good photostability are highly suitable for real-time, in situ, and dynamic imaging at super-resolution using STED nanoscopy.

Conjugated Donor-Acceptor Terpolymers Toward High-Efficiency Polymer Solar Cells.

The development of conjugated alternating donor-acceptor (D-A) copolymers with various electron-rich and electron-deficient units in polymer backbones has boosted the power conversion efficiency (PCE) over 17% for polymer solar cells (PSCs) over the past two decades. However, further enhancements in PCEs for PSCs are still imperative to compensate their imperfect stability for fulfilling practical applications. Meanwhile development of these alternating D-A copolymers is highly demanding in creative design and syntheses of novel D and/or A monomers. In this regard, when being possible to adopt an existing monomer unit as a third component from its libraries, either a D' unit or an A' moiety, to the parent D-A type polymer backbones to afford conjugated D-A terpolymers, it will give a facile and cost-effective method to improve their light absorption and tune energy levels and also interchain packing synergistically. Moreover, the rationally controlled stoichiometry for these components in such terpolymers also provides access for further fine-tuning these factors, thus resulting in high-performance PSCs. Herein, based on their unique features, the recent progress of conjugated D-A terpolymers for efficient PSCs is reviewed and it is discussed how these factors influence their photovoltaic performance, for providing useful guidelines to design new terpolymers toward high-efficiency PSCs.

Salt and water co-assisted exfoliation of graphite in organic solvent for efficient and large scale production of high-quality graphene.

Graphene has attracted enormous attention due to its unique physical properties and attractive applications in many fields. However, it is an ongoing challenge to develop a facile and low-cost method for the large scale preparation of high-quality graphene (HQGr). In this work, we have developed an improved liquid-phase exfoliation method to mass produce HQGr. This method is quite simple but efficient by exfoliation of graphite in organic solvent with the co-assistance of sodium citrate and water. Remarkably, the concentration of as-exfoliated HQGr was as high as 0.71 mg/mL under optimal conditions, while the oxygen content in HQGr was only 2.39%. After annealing at 500 °C for 2 h in argon atmosphere, the mean conductivity of annealed HQGr was as high as 1.4 × 104 S m-1. Therefore, this facile method for liquid-phase exfoliation of graphite has excellent potential in the industrial-scale production of HQGr for numerous applications in energy storage, optical and electronic fields.