Aggregation-induced Emission Luminogens Research Articles

Multiple photofluorochromic luminogens via catalyst-free alkene oxidative cleavage photoreaction for dynamic 4D codes encryption

Controllable photofluorochromic systems with high contrast and multicolor in both solutions and solid states are ideal candidates for the development of dynamic artificial intelligence. However, it is still challenging to realize multiple photochromism within one single molecule, not to mention good controllability. Herein, we report an aggregation-induced emission luminogen TPE-2MO2NT that undergoes oxidation cleavage upon light irradiation and is accompanied by tunable multicolor emission from orange to blue with time-dependence. The photocleavage mechanism revealed that the self-generation of reactive oxidants driving the catalyst-free oxidative cleavage process. A comprehensive analysis of TPE-2MO2NT and other comparative molecules demonstrates that the TPE-2MO2NT molecular scaffold can be easily modified and extended. Further, the multicolor microenvironmental controllability of TPE-2MO2NT photoreaction within polymer matrices enables the fabrication of dynamic fluorescence images and 4D information codes, providing strategies for advanced controllable information encryption.

Catalytic hairpin assembly-based AIEgen/graphene oxide nanocomposite for fluorescence-enhanced and high-precision spatiotemporal imaging of microRNA in living cells

The low abundance, heterogeneous expression, and temporal changes of miRNA in different cellular locations pose significant challenges for both the detection sensitivity of miRNA liquid biopsy and intracellular imaging. In this work, we report an intelligently assembled biosensor based on catalytic hairpin assembly (CHA) and aggregation-induced emission (AIE), named as catalytic hairpin aggregation-induced emission (CHAIE), for the ultrasensitive detection and intracellular imaging of miRNA-155. To achieve such goal, tetraphenylethylene-N3 (TPE-N3) is used as AIE luminogen (AIEgen), while graphene oxide is introduced to quench the fluorescence. When the target miRNA is present, CHA reaction is triggered, causing the AIEgen to self-assemble with the hairpin DNA. This will restrict the intramolecular rotation of the AIEgen and produce a strong AIE fluorescence. Interestingly, CHAIE does not require any enzyme or expensive thermal cycling equipment, and therefore provides a rapid detection. Under optimal conditions, the proposed biosensor can determine miRNA in the concentration range from 2 pM to 200 nM within 30 min, with the detection limit of 0.42 pM. The proposed CHAIE biosensor in this work offers a low background signal and high sensitivity, making it applicable for highly precise spatiotemporal imaging of target miRNA in living cells.

Dynamic Electrostatic Interfacial Engineering for Block Copolymer Microparticles with Reversible Structures.

Responsive nanoparticle surfactants (NPSs) can dynamically and reversibly modulate the interfacial interactions between incompatible components, which are essential in the interfacial catalysis, corrosion, and self-assembly of block copolymers (BCPs). However, NPSs with stimuli-responsive behavior often involve tedious chemical synthesis and surface modifications. Herein, we propose a strategy to in situ construct a kind of dynamic and reversible NPSs by the interfacial electrostatic interaction between the negatively charged nanoparticles (NPs) and the positively charged homopolymers. The NPSs assembled at the oil/water interface reduce the interfacial tension and direct the confined assembly of BCP. Meanwhile, the dynamic NPSs can be disassembled by increasing the pH value or introducing competitive electrostatic attractions, which can dynamically and reversibly change the interfacial properties as well as the alignment of polymer chains, enabling BCP microparticles with reversibly switchable lamellar and cylindrical structures. Furthermore, by the introduction of aggregation-induced emission luminogens as tails to the NPSs, the reversible transformation of BCP microparticles can be visualized by fluorescence emission, which is dependent on the nanostructures of microparticles. This work establishes a concept for dynamically manipulating interfacial interactions and reversibly switching BCP microparticles without time-consuming NPS synthesis, showing promising applications in the fabrication of smart materials with switchable structures and properties.

Multi-stimuli-responsive cyanostilbene derivatives: Their fluorescent and mechanochromic properties, and potential application in water sensing and anti-counterfeiting

In recent years, aggregation-induced emission luminogens (AIEgens) have witnessed numerous groundbreaking advances in fundamental theoretical research and functional applications. Notably, stimuli-responsive AIEgens have achieved remarkable results, demonstrating immense potential for application in various fields such as chemistry, materials science, biology, and medicine. Herein, two multi-stimuli-responsive cyanostilbene derivatives TPE-CNTPA and PH-CNTPA were synthesized by introducing tetraphenylethylene (TPE) and trifluoromethyl groups, respectively. Primarily, under the combined mechanism of aggregation-induced emission (AIE) and twisted intramolecular charge transfer (TICT), TPE-CNTPA and PH-CNTPA exhibit “on-off-on” fluorescent emission characteristics in solution. Secondly, under 365 nm ultraviolet light irradiation, the photo-induced isomerization of PH-CNTPA causes changes in photophysical property, demonstrating its responsiveness to ultraviolet light. In addition, TPE-CNTPA and PH-CNTPA exhibit high-contrast mechanochromic properties, providing broader possibilities for their potential applications in various fields. Moreover, owing to the unique fluorescence emission characteristics, TPE-CNTPA and PH-CNTP have enormous potential for application in the field of encryption anti-counterfeiting. Besides, PH-CNTPA can be utilized for the detection of trace water in single or mixed solvents, demonstrating outstanding sensitivity and anti-interference properties in different solvents. This research work reveals the potential in the fields of water sensing and anti-counterfeiting for these two multi-stimuli-responsive compounds.

Two-Photon Absorption Aggregation-Induced Emission Luminogen/Paclitaxel Nanoparticles for Cancer Theranostics.

Multifaceted nanoplatforms integrating fluorescence imaging and chemotherapy have garnered acknowledgment for their potential potency in cancer diagnosis and simultaneous in situ therapy. However, some drawbacks remain for traditional organic photosensitizers, such as poor photostability, short excitation wavelength, and shallow penetration depth, which will greatly lower the chemotherapy treatment efficiency. Herein, we present lipid-encapsulated two-photon active aggregation-induced emission (AIE) luminogen and paclitaxel (PTX) nanoparticles (AIE@PTX NPs) with bright red fluorescence emission, excellent photostability, and good biocompatibility. The AIE@PTX NPs exhibit dual functionality as two-photon probes for visualizing blood vessels and tumor structures, achieving penetration depth up to 186 and 120 μm, respectively. Furthermore, the tumor growth of the HeLa-xenograft model can be effectively prohibited after the fluorescence imaging-guided and PTX-induced chemotherapy, which shows great potential in the clinical application of two-photon cell and tumor fluorescence imaging and cancer treatment.

Hypoxia-accelerating pyroptosis nanoinducers for promoting image-guided cancer immunotherapy

Precise image-guided cancer immunotherapy holds immense potential in revolutionizing cancer treatment. The strategies facilitating activatable imaging and controlled therapeutics are highly desired yet to be developed. Herein, we report a new pyroptosis nanoinducer that integrates aggregation-induced emission luminogen (AIEgen) and DNA methyltransferase inhibitor with hypoxia-responsive covalent organic frameworks (COFs) for advanced image-guided cancer immunotherapy. We first synthesize and compare three donor-acceptor type AIEgens featuring varying numbers of electron-withdrawing units, and find that the incorporation of two acceptors yields the longest response wavelength and most effective photodynamic therapy (PDT) property, surpassing the performance of analogs with one or three acceptor groups. A COF-based nanoplatform containing AIEgen and pyroptosis drug is successfully constructed via the one-pot method. The intra-COF energy transfer significantly quenches AIEgen, in which both fluorescence and PDT properties greatly enhance upon hypoxia-triggered COF degradation. Moreover, the photodynamic process exacerbates hypoxia, accelerating pyroptosis drug release. The nanoagent enables sensitive delineation of tumor site through in situ activatable fluorescence signature. Thanks to the exceptional ROS production capabilities and hypoxia-accelerating drug release, the nanoagent not only inhibits primary tumor growth but also impedes the progression of distant tumors in 4T1 tumor-bearing mice through potent pyroptosis-mediated immune response. This research introduces a novel strategy for achieving activatable phototheranostics and self-accelerating drug release for synergetic cancer immunotherapy.

A universal strategy for constructing high-performance silica-based AIE materials for biomedical application

As an emerging fluorophore, aggregation-induced emission luminogens (AIEgens) have received widespread attention in recent years, but the inherent drawbacks of AIEgens, such as the poor water-solubility and insufficient fluorescence stability in complex environments, restrict their performance in practical applications. Herein, we report a universal strategy based on hydrophobic dendritic mesoporous silica (HMSN) that can integrate different AIE molecules to construct multi-color fluorescent AIE materials. Specifically, HMSN with central radial pores was used as a powerful carrier for direct loading AIE molecules and restricting their intramolecular motions. Due to the pore-domain restriction effect and hydrophobic interaction, the obtained silica-based AIE materials have bright fluorescence with a maximum quantum yield of 68.38%, high colloidal/fluorescence stability, and excellent biosafety. Further, these silica-based AIE materials can be conjugated with functional antibodies to obtain probes with different targetability. After integration with immunomagnetic beads, the prepared detection probes achieved the quantitative detection of cardiac troponin I with the limit of detection (LOD) of 0.508 ng/mL. Overall, the targeting probes stemming from silica-based AIE materials can not only achieve cell-specific imaging, but quantify the number of Jurkat cells (LOD = 270 cells/mL) to further determine the specific etiology of the disease.

Two polymorphs of a new AIEgen from transition-metal-free cross-coupling reactions: A combined experimental and crystal structure prediction study

We synthesized a new double aromatic pyrrole [2,5-bis(2,5-dimethoxyphenyl)-1H-pyrrole, abbreviated as BDMP] without using transition metals. This compound exhibits a conjugated skeleton, ideal for aggregation-induced emission luminogens (AIEgens). Two methods, Lewis acid catalysis and photoreaction, were used for synthesis. Different methods produce different crystal structures with the same molecular skeleton. The crystals show different AIE properties. The photocatalytically formed crystal (BDMP-B) is highly luminescent with a 10.4 % fluorescence yield. In contrast, the Lewis acid-catalyzed crystal (BDMP-A) has a lower fluorescence yield of 3.0 %. These differences in emission are due to varying crystal packings, confirmed by quantum calculations.To understand these differences, Crystal Structure Prediction (CSP) studies were conducted. Our goal was to find if more stable crystal packings exist. Several energy ranking approaches were used to identify the most feasible polymorphic forms. These approaches include static lattice energy, lattice binding energy, enthalpy, cohesive enthalpy, Gibbs Free Energy, cohesive Gibbs Free Energy, and high-accurate electronic binding energy from large molecule-cluster crystal packings. Our findings suggest that the most stable crystal forms can be predicted accurately using appropriate theoretical methods.This research improves our understanding of AIEgens. It shows the value of combining experimental work with both cost-effective and highly accurate theoretical methods for crystal structure analysis and prediction.

A Ligand-Directed Spatial Regulation to Structural and Functional Tunability in Aggregation-Induced Emission Luminogen-Functionalized Organic-Inorganic Nanoassemblies.

Aggregation-induced emission luminogen (AIEgen)-functionalized organic-inorganic hybrid nanoparticles (OINPs) are an emerging category of multifunctional nanomaterials with vast potential applications. The spatial arrangement and positioning of AIEgens and inorganic compounds in AIEgen-functionalized OINPs determine the structures, properties, and functionalities of the self-assembled nanomaterials. In this work, a facile and general emulsion self-assembly tactic for synthesizing well-defined AIEgen-functionalized OINPs is proposed by coassembling alkane chain-functionalized inorganic nanoparticles with hydrophobic organic AIEgens. As a proof of concept, the self-assembly and structural evolution of plasmonic-fluorescent hybrid nanoparticles (PFNPs) from concentric circle to core shell and then to Janus structures is demonstrated by using alkane chain-modified AuNPs and AIEgens as building blocks. The spatial position of AuNPs in the signal nanocomposite is controlled by varying the alkane ligand length and density on the AuNP surface. The mechanism behind the formation of various PFNP nanostructures is also elucidated through experiments and theoretical simulation. The obtained PFNPs with diverse structures exhibit spatially tunable optical and photothermal properties for advanced applications in multicolor and multimode immunolabeling and photothermal sterilization. This work presents an innovative synthetic approach of constructing AIEgen-functionalized OINPs with diverse structures, compositions, and functionalities, thereby championing the progressive development of these OINPs.

BioAIEgens based on dehydroabietic acid and tetraphenylethene: How does isopropyl group of dehydroabietic acid affect their spectral performance

Based on dehydroabietic acid (DA) derived from natural rosin, two aggregation-induced emission luminogens (BioAIEgens) labeled as 12-DTPA-2pTPE and 13-DTPA-2pTPE were synthesized by introducing tetraphenylethylene (TPE) groups to dehydroabietic acid triarylamine (DTPA). Their structures were optimized, the spectral properties and AIE characteristics were investigated, and the compounds were prepared into nanoparticles (NPs) as fluorescent probes for cell imaging. The results show that the two BioAIEgens have typical AIE characteristics and large Stokes shifts (＞ 120 nm). Due to the electronic and spatial effects of the isopropyl group, the molecular configuration of 12-DTPA-2pTPE is more distorted, and the electron cloud distribution is also different from 13-DTPA-2TPE. The absorption and the emission peaks of 12-DTPA-2TPE are blue-shifted, and the fluorescence quantum yield in the solid is higher. In addition, the 13-DTPA-2TPE nanoparticles (NPs) have low cytotoxicity and good cell imaging effects in vitro.

Enhancing the Luminescence Efficiency of Triphenylamine–Thiophene Aggregation-Induced Emission Luminogens Using Shell-Isolated Nanoparticle-Enhanced Fluorescence (SHINEF)

Enhancing the Luminescence Efficiency of Triphenylamine–Thiophene Aggregation-Induced Emission Luminogens Using Shell-Isolated Nanoparticle-Enhanced Fluorescence (SHINEF)

Cellular senescence imaging and senolysis monitoring in cancer therapy based on a β-galactosidase-activated aggregation-induced emission luminogen

Cellular senescence is a permanent state of cell cycle arrest characterized by increased activity of senescence associated β-galactosidase (SA-β-gal). Notably, cancer cells have been also observed to exhibit the senescence response and are being considered for sequential treatment with pro-senescence therapy followed by senolytic therapy. However, there is currently no effective agent targeting β-galactosidase (β-Gal) for imaging cellular senescence and monitoring senolysis in cancer therapy. Aggregation-induced emission luminogen (AIEgen) demonstrates strong fluorescence, good photostability, and biocompatibility, making it a potential candidate for imaging cellular senescence and monitoring senolysis in cancer therapy when endowed with β-Gal-responsive capabilities. In this study, we introduced a β-Gal-activated AIEgen named QM-β-gal for cellular senescence imaging and senolysis monitoring in cancer therapy. QM-β-gal exhibited good amphiphilic properties and formed aggregates that emitted a fluorescence signal upon β-Gal activation. It showed high specificity towards the activity of β-Gal in lysosomes and successfully visualized DOX-induced senescent cancer cells with intense fluorescence both in vitro and in vivo. Encouragingly, QM-β-gal could image senescent cancer cells in vivo for over 14 days with excellent biocompatibility. Moreover, it allowed for the monitoring of senescent cancer cell clearance during senolytic therapy with ABT263. This investigation indicated the potential of the β-Gal-activated AIEgen, QM-β-gal, as an in vivo approach for imaging cellular senescence and monitoring senolysis in cancer therapy via highly specific and long-term fluorescence imaging. Statement of significanceThis work reported a β-galactosidase-activated AIEgen called QM-β-gal, which effectively imaged DOX-induced senescent cancer cells both in vitro and in vivo. QM-β-gal specifically targeted the increased expression and activity of β-galactosidase in senescent cancer cells, localized within lysosomes. It was cleared rapidly before activation but maintained stability after activation in the DOX-induced senescent tumor. The AIEgen exhibited a remarkable long-term imaging capability for senescent cancer cells, lasting over 14 days and enabled monitoring of senescent cancer cell clearance through ABT263-induced apoptosis. This approach held promise for researchers seeking to achieve prolonged imaging of senescent cells in vivo.

Dual-Functional AIE Fluorescent Probe for Visualization of Lipid Droplets and Photodynamic Therapy of Cancer.

Abnormal lipid droplets (LDs) are known to be intimately bound with the occurrence and development of cancer, allowing LDs to be critical biomarkers for cancers. Aggregation-induced emission luminogens (AIEgens), with efficient reactive oxygen species (ROS) production performance, are prime photosensitizers (PSs) for photodynamic therapy (PDT) with imaging. Therefore, the development of dual-functional fluorescent probes with aggregation-induced emission (AIE) characteristics that enable both simultaneous LD monitoring and imaging-guided PDT is essential for concurrent cancer diagnosis and treatment. Herein, we reported the development of a novel LD-targeting fluorescent probe (TDTI) with AIE performance, which was expected to realize the integration of cancer diagnosis through LD visualization and cancer treatment via PDT. We demonstrated that TDTI, with typical AIE characteristics and excellent photostability, could target LDs with high specificity, which enables the dynamic tracking of LDs in living cells, specific imaging of LDs in zebrafish, and the differentiation of cancer cells from normal cells for cancer diagnosis. Meanwhile, TDTI exhibited fast ROS generation ability (achieving equilibrium within 60 s) under white light irradiation (10 mW/cm2). The cell apoptosis assay revealed that TDTI effectively induced growth inhibition and apoptosis of HeLa cells. Further, the results of PDT in vivo indicated that TDTI had a good antitumor effect on the tumor-bearing mice model. Collectively, these results highlight the potential utility of the dual-functional fluorescent probe TDTI in the integrated diagnosis and treatment of cancer.

Understanding the role of π-π stacking from red carbon for selective, high stable and anti-external interference detecting ferric ions and cellular imaging

The subcarboxylated carbon (C3O2) is a unique molecule that spontaneously polymerizes into highly conjugated fluorescence structures p(C3O2)n, named “red carbon”. This unique property, combined with its role as aggregation-induced emission luminogens, has allowed for a deeper exploration of their emission mechanism. Herein, both density functional theory calculations and experimental approaches to elucidate the crystal structure of π–π stacking in red carbon, thereby enhancing the fluorescence properties of p(C3O2)n polymer in its aggregated state. The time-dependent density functional theory calculations and experimental observations indicate that the fluorescence of red carbon can be quenched by ferric ions (Fe3+) and subsequently restored by ethylenediaminetetraaceticacid (EDTA). This quenching process follows first-order reaction kinetics. On the basis of the coordination to metal ions from abundant heteroatoms on red carbon, the high sensitivity, quick responsive (1 min), sensitive detection (the lowest detection limit is 0.97 μM) for the Fe3+ were realized in red carbon, which provides inspirations for the design of new turn-on probes with high stability in detecting the Fe3+ in aqueous solution. Crucially, the red carbon as a light-up fluorescence probe can be employed for the Fe3+ sensing in living cells, which enlighten a new perspective for designing non-conjugated fluorescent polymers. This innovative approach opens up new avenues for developing probes that can detect Fe3+ with high precision and reliability in complex biological environments.

Reductive prodrug and AIE copolymer nanoparticle for monitoring and chemotherapy

Polymeric micelle systems for drug delivery, monitor and chemotherapy have gained significant attention, and reductive polymeric micelle systems have become particularly attractive due to their controlled release behavior without additional assistance. However, there are challenges in accurately controlling drug and probe release from the nanoparticles and determining the loading content of drug and probe. To address these issues, we have developed a reduction-responsive Pt(IV) prodrug-based polymeric delivery system that can be dynamically monitored using aggregation-induced emission luminogens (AIE) based bioprobes. These polymeric micelle can self-assemble into nanoparticles and release both bio-active Pt(II) drug and bio-probe upon reduction activation. TPE molecules released in the inner endo/lysosomal microenvironment aggregate and fluoresce upon irradiation, thus allowing real-time tracking of drug biodistribution without additional contrast agents. Advantages of this system include position-specific chemical bond cleavage, control of platinum content, and monitoring of drug reduction and biodistribution.

Highly selective and sensitive detection of hyaluronic acid based on a pyrene-cored cationic aggregation-induced emission luminogen

An aggregation-induced emission luminogen (AIEgen) that is positively charged, compound 1, is synthesized by attaching a pyridyl cation to a pyrene core by use of a cyanoethylene bond. By employing compound 1, it is possible to identify hyaluronic acid (HA) by combining it with the negatively charged HA through electrostatic interactions. When combined with HA, compound 1 exhibits a 9-fold fluorescence enhancement within 7 s, and shows a sensitive and quick response to HA with a detection limit as low as 6.9 ng/mL. Among the variety of available biological substances, even analogues to HA such as chondroitin 4-sulfate (CS) and heparin (Hep), compound 1 is shown to have the most significant fluorescence enhancement when connected to HA only, which demonstrates its excellent selectivity for HA. In particular, upon long-wavelength emission close to 600 nm and an extensive shift (∼160 nm), compound 1 allows for a minimization of the auto-fluorescence interference from complex biological substances and creates more accurate outcomes. Finally, the successful application of compound 1 for the purpose of selective and sensitive detection of HA in living cells is shown to be possible. Notably, good linear relationships arise for a serum assay when the concentration of the applied HA is within the range of 0–8.0 μg/mL (R2 = 0.999), which suggests a possible clinical practice for quantifying HA since the clinical dosage level is covered by this range during both cardiovascular surgery and long-term care. Furthermore, our research offers a feasible and straightforward tool for detecting HA through electrostatic interactions.

Boosting Luminescence Efficiency of Near-Infrared-II Aggregation-Induced Emission Luminogens via a Mash-Up Strategy of π-Extension and Deuteration for Dual-Model Image-Guided Surgery.

The simultaneous pursuit of accelerative radiative and restricted nonradiative decay is of tremendous significance to construct high-luminescence-efficiency fluorophores in the second near-infrared wavelength window (NIR-II), which is seriously hindered by the energy gap laws. Herein, a mash-up strategy of π-extension and deuteration is proposed to efficaciously ameliorate the knotty problem. By extending the π-conjugation of the aromatic fragment and introducing an isotope effect to the aggregation-induced emission luminogen (AIEgen), an improved oscillator strength (f), coupled with suppressed deformation and high-frequency oscillation in the excited state, are successively implemented. In this case, a faster rate of radiative decay (kr) and restricted nonradiative decay (knr) are simultaneously achieved. Moreover, the preeminent emissive property of AIEgen in the molecular state could be commendably inherited by the aggregates. The corresponding NIR-II emissive AIEgen-based nanoparticles display high brightness, large Stokes shift, and superior photostability simultaneously, which can be applied for image-guided cancer and sentinel lymph node (SLN) surgery. This work thus provides a rational roadmap to improve the luminescence efficiency of NIR-II fluorophores for biomedical applications.

β-Galactosidase-activated near-infrared AIEgen for ovarian cancer imaging in vivo

Near-infrared (NIR) aggregation induced-emission luminogens (AIEgens) circumvent the noisome aggregation-caused quenching (ACQ) effect in physiological milieu, thus holding high promise for real-time and sensitive imaging of biomarkers in vivo. β-Galactosidase (β-Gal) is a biomarker for primary ovarian carcinoma, but current AIEgens for β-Gal sensing display emissions in the visible region and have not been applied in vivo. We herein propose an NIR AIEgen QM-TPA-Gal and applied it for imaging β-Gal activity in vitro and in ovarian tumor model. After being internalized by ovarian cancer cells (e.g., SKOV3), the hydrophilic nonfluorescent QM-TPA-Gal undergoes hydrolyzation by β-Gal to yield hydrophobic QM-TPA-OH, which subsequently aggregates into nanoparticles to turn NIR fluorescence “on” through the AIE mechanism. In vitro experimental results indicate that QM-TPA-Gal has a sensitive and selective response to β-Gal with a limit of detection (LOD) of 0.21 U/mL. Molecular docking simulation confirms that QM-TPA-Gal has a good binding ability with β-Gal to allow efficient hydrolysis. Furthermore, QM-TPA-Gal is successfully applied for β-Gal imaging in SKOV3 cell and SKOV3-bearing living mouse models. It is anticipated that QM-TPA-Gal could be applied for early diagnosis of ovarian cancers or other β-Gal-associated diseases in near future.

Anion-π+ AIEgens for Fluorescence Imaging and Photodynamic Therapy.

Fluorescence imaging-guided photodynamic therapy (PDT) has attracted extensive attention due to its potential of real-time monitoring the lesion locations and visualizing the treatment process with high sensitivity and resolution. Aggregation-induced emission luminogens (AIEgens) show enhanced fluorescence and reactive oxygen species (ROS) generation after cellular uptake, giving them significant advantages in bioimaging and PDT applications. However, most AIEgens are unfavorable for the application in organisms due to their severe hydrophobicity. Anion-π+ type AIEgens carry intrinsic charges that can effectively alleviate their hydrophobicity and improve their binding capability to cells, which is expected to enhance the bioimaging quality and PDT performance. This concept summarizes the applications of anion-π+ type AIEgens in fluorescence imaging, fluorescence imaging-guided photodynamic anticancer and antimicrobial therapy in recent years, hoping to provide some new ideas for the construction of robust photosensitizers. Finally, the current problems and future challenges of anion-π+ AIEgens are discussed.

Tuning Molecular Packing by Twisting Structure to Facilely Construct Highly Efficient Solid‐State Fluorophores for Two‐Photon Bioimaging and Photodynamic Therapy

AbstractThe traditional design strategy for constructing highly bright solid‐state luminescent materials relies on incorporating aggregation‐induced emission (AIE) scaffolds, molecular rotors, or bulky substituents to prevent close cofacial packing, which limits the strategy diversity in developing new materials. Herein, a strategy of tuning molecular packing by twisting molecular structure of conventional aggregation‐caused quenching fluorophore is proposed to endow materials with AIE effect and enhance the solid‐state fluorescence. Accordingly, a series of 1,4‐bis(diphenylamino)‐2,5‐disubstituted benzene fluorophores exhibiting AIE characteristics, high solid‐state fluorescence efficiency (up to 0.99), wide emission color tunability, and good near‐infrared (NIR) two‐photon absorption is facilely developed. All these luminogens can specifically stain intracellular lipid droplets with a high signal‐to‐noise ratio, high biocompatibility, and good photostability. Besides, the luminogens exhibit effective reactive oxygen species (ROS) generation capability upon low‐power white light irradiation. Among them, the AIE luminogen, named BDBDC, integrating the NIR emission, good NIR two‐photon absorption and strongest ROS generation demonstrates superior performances in two‐photon fluorescence imaging of various tissues and photodynamic cancer therapy. This molecular design philosophy provides a new way of designing highly bright solid‐state fluorophores for practical applications.