Aggregation-induced Emission Luminogens Research Articles

Hexagonal Prism-Shaped AIE-Active MOFs as Coreactant-Free Electrochemiluminescence Luminophores Coupled with Hollow Cu2-xO@Pd Heterostructures as Efficient Quenching Probes for Sensitive Biosensing.

For most self-luminous metal-organic framework (MOF)-involved electrochemiluminescence (ECL) systems, the integration of exogenous coreactants is indispensable to promote ECL efficiency. However, the introduction of a coreactant into an electrolyte would result in poor stability, thereby inevitably affecting analytical accuracy. Herein, by employing aggregation-induced emission luminogens as ligands, we first synthesized one hexagonal prism-shaped MOF that displays robust and steady ECL signal without an exogenous coreactant. Furthermore, adenosine triphosphate (ATP), as the target analyte, can be fixed on the electrode surface directly owing to the strong coordination between Zr4+ and phosphate groups. According to the ECL resonance energy transfer effect, hollow Cu2-xO@Pd heterostructures are conveniently prepared and act as efficient quenching probes. Remarkably, the resultant urchin-like hollow structure could provide more active sites to anchor ATP aptamers, thus enhancing the ECL quenching efficiency. In this manner, an elaborate coreactant-free ECL system was developed to detect ATP, which demonstrates a remarkable detection limit of 0.17 nM, as well as excellent stability and reproducibility. The present work offers significant enlightenment for the further evolution of advanced ECL systems integrated with MOF-based luminophores.

A water-soluble aggregation-induced emission luminogen for NIR-I/NIR-II fluorescence imaging of breast cancer bone metastases

Advanced breast cancer is prone to bone metastasis, which is the most common bone metastatic tumor. Current clinical methods for diagnosing breast cancer bone metastases rely on serological markers, computed tomography and magnetic resonance imaging. However, these technologies cannot meet patients' needs due to the delayed screening, complex procedures and expensive equipment. Optical imaging currently exhibits inexhaustible and vigorous vitality in the field of diagnosis thanks to its advantages of simplicity, good controllability and high resolution. Nevertheless, the development of prominent chromophores for the diagnosis of breast cancer bone metastases is an appealing yet significantly challenging task. In this contribution, we rationally designed and synthesized three water-soluble aggregation-induced emission (AIE) luminogens, named PEGTPA-BTD, PEGTPA-NTD, and PEGTPA-NSD, by introducing different moieties as electron acceptors and PEGylated triphenylamine derivatives as electron donors and hydrophilic moieties. In vitro experiments showed that PEGTPA-NSD has a longer absorption and emission wavelength, where the emission wavelength can extend into NIR-II region. Besides, PEGTPA-NSD could self-assemble into stable nanoparticles in aqueous solution. Cell experiments showed that PEGTPA-NSD had no obvious dark toxicity to tumor cells or normal cells, and were easily taken in by tumor cells for cell imaging. What's more, PEGTPA-NSD NPs possessed excellent fluorescence imaging performance and biocompatibility in vivo for breast cancer bone metastases in NIR-I and NIR-II region, respectively. In summary, PEGTPA-NSD is the first reported aggregation-induced emission luminogens (AIEgens) that can self-assemble to nanoparticles in aqueous solution for NIR-I/NIR-II fluorescence imaging of breast cancer bone metastases. These findings would provide new strategies for optical diagnostic imaging of breast cancer bone metastases to better advance clinical technology development.

AIE-active fluorescence emitters containing tetraphenylethylene and α-cyanostilbene with mechanochromism and photo-responsive behaviors

Aggregation induced emission luminogens (AIEgens) as one of the optimal alternatives for designing stimuli-responsive fluorophores for real-life applications have sparked much current interest in smart materials design. Herein, the “Star molecules” in AIEgens of α-cyanostilbene and Tetraphenylethylene (TPE) derivatives were constructed into one molecular, namely DC-TPE-tBu and DC-TPE-CN. Both compounds exhibited significant AIE properties. Moreover, the two compounds could change their luminescent colors and intensities under the stimulation of external mechanical force and UV light, showing excellent mechanochromic luminescent (MCL) and remarkable photo-responsive behaviors, respectively. The stimuli responsive mechanisms were investigated by powder X-Ray diffractometer (PXRD) spectra and density functional theory calculations (DFT). The MLC behaviors were associated with the crystalline-to-amorphous transitions after mechanical grinding. These remarkable features make them suitable for the application of mechano/photo-sensors. The studies provide a useful strategy for developing AIE-active functional materials.

Traffic signal-inspired fluorescence lateral flow immunoassay utilizing self-assembled AIENP@Ni/EC for simultaneous multi-pesticide residue detection

The presence of multiple pesticide residues in fruits and vegetables poses a serious threat to human health. Conventional gold nanoparticles (AuNPs) used in multiplex lateral flow immunoassays (M−LFIA) often exhibit poor sensitivity and potential for misidentification. This study introduces a traffic signal-inspired fluorescent LFIA (T-FLFIA) designed for the simultaneous quantitative detection of chlorothalonil (CTN), paclobutrazol (PBZ), and fipronil (FIP) in cowpea and apple samples. Utilizing the hydrophobic interactions of aggregation-induced emission luminogens (AIEgens) and the coordination of epicatechin (EC) with Ni2+, we developed a novel nanostructure-aggregation-induced emission nanoparticle (AIENP) coated with a metal-polyphenol network of Ni/EC (AIENP@Ni/EC) via a self-assembly method and employed it as fluorescence probe in T-FLFIA. Three distinct colors of AIENP@Ni/EC featuring green, yellow, and red fluorescence were successfully synthesized by coating various AIEgens. This multicolor fluorescence capability facilitates more precise and expedited discrimination among multiple detection targets. High-performance AIE fluorescence probes were fabricated by directly coupling AIENP@Ni/EC with different antibodies through electrostatic interactions, leveraging the exceptional biocompatibility of Ni/EC. The T-FLFIA exhibited sensitive detection of CTN, PBZ, and FIP at concentrations as low as 0.038 ng/mL, 0.025 ng/mL, and 0.046 ng/mL, respectively, with high qualitative accuracy (92.5 %) within a rapid timeframe (5 s). This exceptional performance can be attributed to its outstanding optical properties and distinguishable colors. This approach demonstrated enhanced sensitivity and accuracy, reduced consumption of antibodies and immunoprobes, and a broader detection range compared to single-color AuNPs-M−LFIA. This study introduces a novel, practical, and cost-effective tool for rapid screening of diverse pesticide residues in field settings

4,4'-Sulfonyldianiline Derived Aggregation-Induced Emission Luminogen for the Detection of Ofloxacin.

The excessive use of antibiotic ofloxacin (Oflx) can cause serious detrimental effects to human health. Therefore, the utmost research priority is required to develop facile methods to detect Oflx. Herein, a V-shaped aggregation-induced emission (AIE) active Schiff base SDANA was introduced for the fluorescent turn-on detection of Oflx. The Schiff base SDANA was synthesized by condensing 4,4'-sulfonyldianiline with two equivalents of 2-hydroxy-1-naphthaldehyde. The nearly non-fluorescent SDANA in DMSO showed strong orange emission with the increase in HEPES buffer (H2O, 10 mM, pH 7.4) fractions in DMSO from 70 %-95 % due to the combined effects of AIE and ESIPT. The DLS and SEM analyses were performed to complement the formation of self-aggregates of SDANA. With the addition of Oflx, the fluorescence emission of AIE luminogen (AIEgen) SDANA (λem=575 nm, λex=400 nm) was blue-shifted and enhanced at 530 nm. The interactions of Oflx over the surface of SDANA aggregates disrupted the intramolecular charge transfer and aggregation morphology of SDANA, which gave a distinct fluorescence response to detect Oflx. The detection limit for Oflx was estimated as 0.81 μM, and the developed probe AIEgen SDANA was applied for the quantification of Oflx in human blood serum.

Multicomponent Diversity-Oriented Access to Boronic-Acid-Derived Pyrrolide Salicyl-Hydrazone Fluorophores with Strong Solid-State Emission.

Fluorescent molecular platforms are highly sought after for their applications in biology and optoelectronics but face challenges with solid-state emission quenching. To address this, bulky substituents or aggregation-induced emission luminogens to restrict intramolecular motion are used to enhance the brightness. Here, we have successfully engineered a novel class of boron complexed pyrrolide salicyl-hydrazone fluorophores named BPSHY. These dyes were synthesized through a diversity-oriented condensation of pyrrole and salicylaldehyde derivatives combined with various aromatic boronic acids. The resulting 3D structures, owing to bulky boron axially substituted aryl groups, impart excellent solubility in a variety of solvents. Significantly, the BPSHY dyes exhibit strong absorption in the visible region and remarkably large Stokes shifts. Crucially, they demonstrate intense emission in aqueous solutions due to aggregation-induced emission effects. In solid-states, these dyes achieve high quantum yields, reaching up to 58%. Further expanding their utility, we developed two new BPSHY probes: one incorporating morpholine and another containing triphenylphosphine salt. Both of them are found to specifically label subcellular organelles such as lysosomes and mitochondria within live cells. Notably, these probes demonstrate exceptional staining efficacy and two-photon fluorescence feature. This highlights the considerable promise of BPSHY fluorophores for monitoring and visualizing the dynamic transformations of organelles.

Synergistically Activated Aggregation-Induced Emission Probe for Precise In Situ Staining of Lipids in Atherosclerotic Plaques.

Visualizing the localization and distribution of lipids within arteries is crucial for studying atherosclerosis. However, existing lipid-specific probes face challenges such as strong hydrophobicity and nonspecific staining of lipophilic organelles or tissues, making them impractical for the precise identification of atherosclerotic plaques. To address this issue, we design a synergistically activated probe, Cbz-Lys-Lys-TPEB, which responds to cathepsin B (CTB) and H2O2 for the in situ generation of aggregation-induced emission luminogens (AIEgens). This enables specific staining of lipids within arteries and precise imaging of atherosclerotic plaques. The probe combines a tetraphenylethene building block with a hydrophilic peptide sequence (Cbz-Lys-Lys) and phenylboric acid module, providing excellent water solubility and fluorescence quenching in a molecular dispersion state. Upon interaction with H2O2 and CTB within plaques, the hydrophilic Cbz-Lys-Lys-TPEB probe is specifically cleaved and converted into hydrophobic AIEgens, leading to rapid aggregation and significant fluorescence enhancement. Interestingly, the in situ-liberated AIEgens display distinct lipid binding ability, effectively tracking the location and distribution of lipids in plaques. This synergistic target-activated AIEgen liberation strategy demonstrates significant feasibility for the reliable and accurate identification of atherosclerotic plaques, holding tremendous potential for clinical diagnosis and risk stratification of atherosclerosis.

AIE Active Imidazole-Stilbene Conjugated Fluorescent Probes: Illuminating Latent Fingerprints and Advancing Anticounterfeiting Technologies.

Aggregation-induced emission luminogens (AIEgens) are widely used in the realm of latent fingerprint visualization owing to their luminosity and resistance to photobleaching. However, challenges such as significant background interference and limited resolution hinder their rapid advancement. Consequently, there is a pressing need to improve the detailed visualization of latent fingerprint (LFP) imaging, particularly for analyzing level 3 details. To address this, we have designed donor-acceptor (D-A) type AIEgens named MMIMV, DMIMV, and TMIMV. These compounds exhibit robust emissions ranging from 481 to 552 nm and signify positive fluorosolvatochromism. When applied as powder dusting, these derivatives enable the fluorescence imaging of LFPs on various material substrates. The analysis of these imaged LFPs yields intricate details regarding fingerprint ridge patterns. Our results underscore the potential of highly emissive AIEgens MMIMV, DMIMV, and TMIMV as promising candidates for fingerprint visualization, thus offering significant implications for forensic investigations. Furthermore, these derivatives serve as effective fluorescent security inks for writing and drawing, presenting a novel avenue for robust anticounterfeiting applications.

Rigidifying aggregation-induced emission luminogens by metal–organic framework formation for sensitive lateral flow immunoassay

T-2 toxin, the strongest toxic of type A trichothecenes, widely exists in barley, wheat, corn, oats, and even human food, which is urgent to establish a rapid and sensitive detection method for T-2 toxin. Herein, we developed a fluorescent lateral flow immunoassay (LFIA) for sensitive detection of T-2 toxin. Specially, the monoclonal antibody (mAb) was prepared by immunizing mice and cell fusion, and exhibited a low half maximal inhibitory concentration (IC50) of 0.482 ng mL−1. In addition, an aggregation-induced emission (AIE)-based metal-organic framework (HfMOFs) with excellent fluorescence performance (QY: 72.5 %) was developed as reporter. Benefiting from these advantages, the limit of detection (LoD) of HfMOFs-LFIA was 0.0487 ng mL−1, which was 7.7-fold lower than traditional nanoparticles-based LFIA (0.375 ng mL−1). In addition, HfMOFs-LFIA was used for the detection of T-2 toxin in actual samples and showed satisfactory recoveries (71.3 %–123.7 %) with coefficient of variation (2.96 %–14.07 %). Overall, the dual-improvement in mAb and label might power the development in LFIA, achieving innovative prospects for LFIA in food safety fields.

Aggregation-Induced Emission Luminogen Based Wearable Visible-Light Penetrator for Deep Photodynamic Therapy.

Photodynamic therapy (PDT) has emerged as a preferred nonsurgical treatment in clinical applications due to its capacity to selectively eradicate diseased tissues while minimizing damage to normal tissue. Nevertheless, its clinical efficacy is constrained by the limited penetration of visible light. Although near-infrared (NIR) lasers offer enhanced tissue penetration, the dearth of suitable photosensitizers and a pronounced imaging-treatment disparity pose challenges. Additionally, clinical implementation via optical fiber implantation carries infection risks and necessitates minimally invasive surgery, contradicting PDT's noninvasive advantage. In this study, we introduce a brilliant approach utilizing aggregation-induced emission luminogens (AIEgen) to develop a visible-light penetrator (VLP), coupled with wireless light emitting diodes (LEDs), enabling deep photodynamic therapy. We validate the therapeutic efficacy of this visible-light penetrator in tissues inaccessible to conventional PDT, demonstrating significant suppression of inflammatory diffusion in vivo using AIEgen TBPPM loaded within the VLP, which exhibits a transmittance of 86% in tissues with a thickness of 3 mm. This innovative visible-light penetrator effectively overcomes the substantial limitations of PDT in clinical settings and holds promise for advancing phototherapy.

Reengineering of Donor-Acceptor-Donor Structured Near-Infrared II Aggregation-Induced Emission Luminogens for Starving-Photothermal Antitumor and Inhibition of Lung Metastasis.

Electron acceptor possessing strong electron-withdrawing ability and exceptional stability is crucial for developing donor-acceptor-donor (D-A-D) structured aggregation-induced emission luminogens (AIEgens) with second near-infrared (NIR-II) emission. Although 6,7-diphenyl-[1,2,5] thiadiazolo [3,4-g] quinoxaline (PTQ) and benzobisthiadiazole (BBT) are widely employed as NIR-II building blocks, they still suffer from limited electron-withdrawing capacity or inadequate chemo-stability under alkaline conditions. Herein, a boron difluoride formazanate (BFF) acceptor is utilized to construct NIR-II AIEgen, which exhibits a better overall performance in terms of NIR-II emission and chemo-stability compared to the PTQ- and BBT-derived fluorophores. With finely tuned intramolecular motions and strong D-A interaction strength, TPE-BFF simultaneously exhibits high molar extinction coefficient (ε= 4.31 × 104 M-1cm-1), strong NIR-II emission (Φ = 0.49%) and photothermal effect (η = 58.5%), as well as high stability. Thanks to these merits, the thermosensitive nanoparticles constructed by integrating TPE-BFF and the antiglycolytic agent 2-deoxy-d-glucose (2DG) are successfully utilized for imaging-guided photothermal antitumor lung metastasis by regulating glycolysis and reducing ATP-dependent heat shock proteins. Combining experimental results and theoretical calculations, BFF proves to be an outstanding electron acceptor for the design of versatile NIR-II AIEgens. Overall, this study offers a promising alternative for developing multifunctional NIR-II AIEgens in biomedical applications.

Scaffold-Free Efficient Light-Harvesting Nanoparticles Based on One-Pot Self-Assembly of Donor–Acceptor Aggregation-Induced Emission Luminogens

Scaffold-Free Efficient Light-Harvesting Nanoparticles Based on One-Pot Self-Assembly of Donor–Acceptor Aggregation-Induced Emission Luminogens

Tetraphenylethene-Based Ni8-Pyrazolate Metal-Organic Framework for Photoredox/Nickel Dual Catalysis of C-S Cross-Coupling.

As a prototypical aggregation-induced emission luminogen (AIEgen), the tetraphenylethene (TPE) moiety has been judiciously modified as organic linkers for constructing various functional metal-organic frameworks (MOFs). However, these AIEgen-based MOFs have rarely received research attention in photocatalytic applications due to their limited stability in harsh reaction conditions. In this work, we report a robust Ni8-pyrazolate-based MOF (denoted as TPE4Pz-Ni) under the guidance of reticular chemistry, which is assembled by an AIE-active tetratopic linker of 1,1,2,2-tetrakis(4-(1H-pyrazol-4-yl)phenyl)ethane (H4-TPE4Pz) with a 12-connected Ni8-cluster of [Ni8(OH)4(H2O)2Pz12] (Pz = pyrazolate) in a (4,12)-connected ftw-a topological network. Notably, MOF TPE4Pz-Ni exhibits excellent stability in a wide range of solvents and even in a saturated NaOH solution. Moreover, its luminescent emission is effectively quenched via a ligand-to-metal charge transfer (LMCT) process originating from the TPE-cored linker to the Ni8 cluster, which enables TPE4Pz-Ni to act as an efficient photoredox/nickel dual catalyst for light-mediated C-S cross-coupling reactions between various aryl iodides and thiols.

Aggregation-Induced Emission Luminogen: Role in Biopsy for Precision Medicine.

Biopsy, including tissue and liquid biopsy, offers comprehensive and real-time physiological and pathological information for disease detection, diagnosis, and monitoring. Fluorescent probes are frequently selected to obtain adequate information on pathological processes in a rapid and minimally invasive manner based on their advantages for biopsy. However, conventional fluorescent probes have been found to show aggregation-caused quenching (ACQ) properties, impeding greater progresses in this area. Since the discovery of aggregation-induced emission luminogen (AIEgen) have promoted rapid advancements in molecular bionanomaterials owing to their unique properties, including high quantum yield (QY) and signal-to-noise ratio (SNR), etc. This review seeks to present the latest advances in AIEgen-based biofluorescent probes for biopsy in real or artificial samples, and also the key properties of these AIE probes. This review is divided into: (i) tissue biopsy based on smart AIEgens, (ii) blood sample biopsy based on smart AIEgens, (iii) urine sample biopsy based on smart AIEgens, (iv) saliva sample biopsy based on smart AIEgens, (v) biopsy of other liquid samples based on smart AIEgens, and (vi) perspectives and conclusion. This review could provide additional guidance to motivate interest and bolster more innovative ideas for further exploring the applications of various smart AIEgens in precision medicine.

Organophosphorus Hydrolase-like Nanozyme with an Activity-Quenched Aggregation-Induced Emission Effect: A Self-Reporting and Specific Assay of Nerve Agents.

Given the promising prospect of aggregation-induced emission luminogens (AIEgens) in fluorescence assays, it is interesting and significant to endow AIEgens with molecular recognition capability (such as enzyme-like activity). Here, an AIE nanomaterial with intrinsic enzyme-like activity (named as "AIEzyme") is designed and synthesized via a facile coordination polymerization of Zr4+ and AIE ligands. AIEzyme possesses enhanced and stable fluorescence in different solvents because of the AIE effect of ligands in the rigid structure of a coordination polymer. On the other hand, the organophosphorus hydrolase (OPH)-mimicking activity of AIEzyme exhibits excellent affinity and specific activity. Interestingly, the OPH-like activity can quench the inherent fluorescence of AIEzyme by the hydrolysate of a typical organophosphorus nerve agent (OPNA), diethyl-4-nitrophenylphosphate. Due to the sensitive activity-induced quenching effect for AIE, the self-reporting fluorescence assay method based on AIEzyme was established, which shows ultrahigh sensitivity, high selectivity, good storage stability, and acceptable reliability for a real sample assay. Moreover, the simultaneous colorimetric method broadens the detection range and the application scenarios. The proposed assay method avoided the interference of O2 during detection because the OPH-like activity does not derive from the generation of ROS. As a bonus, AIEzyme can also be used for the degradation of OPNAs by OPH-like activity, and the process can be self-monitored by AIE quenching. This work would provide a new opportunity for expanding the application of AIEgens and artificial enzymes by endowing AIEgens with enzyme-like activity.

CRISPR/Cas-mediated “one to more” lighting-up nucleic acid detection using aggregation-induced emission luminogens

CRISPR diagnostics are effective but suffer from low signal transduction efficiency, limited sensitivity, and poor stability due to their reliance on the trans-cleavage of single-stranded nucleic acid fluorescent reporters. Here, we present CrisprAIE, which integrates CRISPR/Cas reactions with “one to more” aggregation-induced emission luminogen (AIEgen) lighting-up fluorescence generated by the trans-cleavage of Cas proteins to AIEgen-incorporated double-stranded DNA labeled with single-stranded nucleic acid linkers and Black Hole Quencher groups at both ends (Q-dsDNA/AIEgens-Q). CrisprAIE demonstrates superior performance in the clinical nucleic acid detection of norovirus and SARS-CoV-2 regardless of amplification. Moreover, the diagnostic potential of CrisprAIE is further enhanced by integrating it with spherical nucleic acid-modified AIEgens (SNA/AIEgens) and a portable cellphone-based readout device. The improved CrisprAIE system, utilizing Q-dsDNA/AIEgen-Q and SNA/AIEgen reporters, exhibits approximately 80- and 270-fold improvements in sensitivity, respectively, compared to conventional CRISPR-based diagnostics. We believe CrisprAIE can be readily extended as a universal signal generation strategy to significantly enhance the detection efficiency of almost all existing CRISPR-based diagnostics.

AIEgens-based luminescent metal-organic frameworks as novel electrochemiluminescence emitters Integrated with co-reaction amplification strategy for CA15-3 detection

A current research focus in the field of electrochemiluminescence (ECL) is the development of novel high-performance emitters. Herein, we reported the synthesis of a zirconium-based metal–organic framework (Zr-TBAPy-MOF) using the aggregation-induced emission luminogens (AIEgens) 1,3,6,8-tetra(4-carboxyphenyl)pyrene (H4TBAPy) as ligands and Zr6-clusters as nodes. The resulting AIE-active luminescent MOF (AIE-LMOF) exhibited superior ECL properties and was used as an ECL emitter to construct a high-sensitivity ECL immunosensor. Conceptual experiments demonstrated that Zr-TBAPy-MOF showed significantly stronger ECL emission compared to both the monomers and aggregates of H4TBAPy, attributed to the effective restriction of intramolecular motion (RIM). On the sensor substrate, we designed an Au@ZnO/Cu2O nanocomposite as a co-reactant accelerator. This significantly promoted the generation of sulfate radicals (SO4•−) from persulfate (S2O82−) through the sustainable switching of Cu+/Cu2+ oxidation states in copper oxide (Cu2O). Additionally, zinc oxide (ZnO), which had excellent electrochemical properties, further enhanced the catalytic activity of the materials. Leveraging these advantages, we developed a sandwich-type ECL immunosensor for the ultrasensitive detection of carbohydrate antigen 15–3 (CA15-3), demonstrating a wide sensitive range (0.001 − 100 U/mL) and a low detection limit (0.0007 U/mL). Overall, this work paves the way for the development of efficient ECL luminophores with significant potential in the field of immunoassays for the early diagnosis of disease.

Aggregation-induced emission luminogens for intracellular bacteria imaging and elimination

Intracellular bacterial infections are a serious threat to human health due to their ability to escape immunity and develop drug resistance. Recent attention has been devoted to identifying and ablating intracellular bacteria with fluorescence probes. Aggregation-induced emission luminogens (AIEgens) photosensitizers as fluorescence probes possess excellent photostability and rapid response, which have emerged as powerful fluorescent tools for intracellular bacterial detection and antibacterial therapy. This review is intended to highlight the current advances in AIEgens on intracellular bacteria imaging and elimination, which covers topics from intracellular AIE mechanism, intracellular bacteria imaging of AIEgens to the elimination of intracellular bacteria with AIEgens. AIEgens utilized different interactions to detect intracellular bacteria, emitting bright light due to restricted intramolecular movement to visualize intracellular bacteria. Photosensitive AIEgens generate reactive oxygen species (ROS) in the aggregate state to elimate intracellular bacteria. Moreover, the prospects and application of AIEgens in intracellular bacteria imaging and elimination are also discussed, which provides insights for the development of AIE-based diagnostic and therapeutic materials and technologies.

Engineering AIEgens-Tethered Gold Nanoparticles with Enzymatic Dual Self-Assembly for Amplified Cancer-Specific Phototheranostics.

Accurate imaging and precise treatment are critical to controlling the progression of pancreatic cancer. However, current approaches for pancreatic cancer theranostics suffer from limitations in tumor specificity and invasive surgery. Herein, a pancreatic cancer-specific phototheranostic modulator (AuHQ) dominated by aggregation-induced emission (AIE) luminogens-tethered gold nanoparticles is meticulously designed to facilitate prominent fluorescence-photoacoustic bimodal imaging-guided photothermal immunotherapy. Once reaching the pancreatic tumor microenvironment (TME), the peptide Ala-Gly-Phe-Ser-Leu-Pro-Ala-Gly-Cys (AGFSLPAGC) linkage within AuHQ can be specifically cleaved by the overexpressed enzyme Cathepsin E (CTSE), triggering the dual self-assembly of AuNPs and AIE luminogens. The aggregation of AuNPs mediated by enzymatic cleavage results in potentiated photothermal therapy (PTT) under near-infrared (NIR) laser irradiation, induced immunogenic cell death (ICD), and enhanced photoacoustic imaging. Simultaneously, AIE luminogen aggregates formed by hydrophobic interaction can generate AIE fluorescence, enabling real-time and specific fluorescence imaging of pancreatic cancer. Furthermore, coadministration of an indoleamine 2,3-dioxygenase 1 (IDO1) inhibitor with AuHQ can address the limitations of PTT efficacy imposed by the immunosuppressive TME and leverage the synergistic potential to activate systemic antitumor immunity. Thus, this well-designed phototheranostic modulator AuHQ facilitates the intelligent enzymatic dual self-assembly of imaging and therapeutic agents, providing an efficient and precise approach for pancreatic cancer theranostics.

Ultrafast dynamics and electroluminescence performance of a novel tetraphenylethylene-based aggregation induced emission luminogen

Efficient emission and confined molecular conjugation in aggregated/solid form, are two beneficial characteristics of blue organic light-emitting materials (OLEMs). Aggregation-induced emission molecules (AIEgens) have evolved as auspicious OLEMs that possess these properties. Herein, we discover an innovative sky-blue tetraphenylethene-based AIEgen, 4′,4‴-(1-phenyl-2-(4-(1,2,2-triphenylvinyl)phenyl)-1H-imidazole-4,5-diyl)bis(N,N-diphenyl-[1,1′-biphenyl]-4-amine) (2TPA-ITPE), with high thermal stability. By employing this AIEgen as a non-doped emitter, the constructed organic light-emitting diode demonstrates a maximum external quantum efficiency of 3.35 % with a power efficiency of 4.1 lm/W and high luminescence of 15896.92 cd/m2 2TPA-ITPE exhibits a weak donor-acceptor character. Moreover, to probe the photo-physical nature of this AIEgen, its excited-state dynamics are examined through ultrafast transient absorption spectroscopy (TAS). The TAS results of this OLEM unveil the generation of a resonant structure species owing to the elongation of C=C double bond. The excited state dynamics reveal that 2TPA-ITPE undergoes three processes after excitation (internal conversion, C=C elongation and vibrational cooling). These findings offer innovative insights into the ultrafast mechanisms underlying excited TPE-based OLEMs.