Aggregation-induced Emission Characteristics Research Articles

All-thiophene dendrimers based on cyclooctatetrathiophene: synthesis and aggregation-induced emission (AIE) features

A novel class of all-thiophene dendrimers with obvious AIE emissions was designed and synthesized based on saddle-shaped cyclooctatetrathiophene (COTh) as building blocks.

Near-infrared aggregation-induced emission characteristics of new o-carborane fluorophores with large stokes shifts and self-recovering mechanochromic luminescence

o-Carborane fluorophores with large Stokes shifts (>14 000 cm−1) near-infrared AIE characteristics and self-recovering mechanochromic luminescence.

Aggregation-induced emission-active iridium (III)-based mitochondria-targeting nanoparticle for two-photon imaging-guided photodynamic therapy

The efficacy of imaging-guided photodynamic therapy (PDT) is compromised by the attenuation of fluorescence and decline in reactive oxygen species (ROS) generation efficiency in the physiological environment of conventional photosensitizers, limited near-infrared (NIR) absorption, and high systemic cytotoxicity. This paper presents the synthesis of two cyclometalated Ir (III) complexes (Ir-thpy and Ir-ppy) by using a triphenylamine derivative (DPTPA) as the primary ligand and their encapsulation into an amphiphilic phospholipid to form nanoparticles (NPs). These complexes exhibit aggregation-induced emission features and remarkably enhanced ROS generation compared to Chlorin e6 (Ce6). Moreover, Ir-thpy NPs possess the unique ability to selectively target mitochondria, leading to depolarization of the mitochondrial membrane potential and ultimately triggering apoptosis. Notably, Ir-thpy NPs exhibit exceptional photocytotoxicity even towards cisplatin-resistant A549/DDP tumor cells. In vivo two-photon imaging verified the robust tumor-targeting efficacy of Ir-thpy NPs. The in vivo results unequivocally demonstrate that Ir-thpy NPs exhibit excellent tumor ablation along with remarkable biocompatibility. This study presents a promising approach for the development of multifunctional Ir-NPs for two-photon imaging-guided PDT and provides novel insights for potential clinical applications in oncology.

Schiff base fluorescent sensor with aggregation induced emission characteristics for the sensitive and specific Fe3+ detection

An aggregation induced emission based compound ((E)-4-((2-hydroxy-5-methoxybenzylidene)amino)benzoic acid) was synthesized through facile Schiff base condensation and characterized by various spectral techniques. The as-prepared compound represented a typical aggregation induced emission behavior in aqueous solution and exploited as a turn-off fluorescent sensor for Fe3+ detection in THF-H2O system (3:7, v/v) with high sensitivity and selectivity. The mechanism of the fluorescence quenching was intensively studied, which was attributed to both dynamic quenching and inner filter effect. The fluorescence probe displayed a highly broad dynamic response range (0.5–500 μM) for selective detection of Fe3+ with a limit of detection of 0.079 μM. The proposed method was successfully employed for detection and quantification of Fe3+ in human urine samples and proved to have potential for practical applications in biological field.

Molecular Engineering Modulating the Singlet-Triplet Energy Splitting of Indolocarbazole-Based TADF Emitters Exhibiting AIE Properties for Nondoped Blue OLEDs with EQE of Nearly 20.

The development of efficient blue thermally activated delayed fluorescence (TADF) emitters with an aggregation-induced emission (AIE) nature, for the construction of organic light-emitting diodes (OLEDs), is still insufficient. This can be attributed to the challenges encountered in molecular design, including the inherent trade-off between radiative decay and reverse intersystem crossing (RISC), as well as small singlet-triplet energy splitting (ΔEST) and the requirement for high photoluminescence quantum yields (ΦPL). Herein, we present the design of three highly efficient blue TADF molecules with AIE characteristics by combining π-extended donors with different acceptors to modulate the differences in the electron-donating and electron-withdrawing abilities. This approach not only ensures high emission efficiency by suppressing close π-π stacking, weakening nonradiative relaxation, and enhancing radiative transition but also maintains the equilibrium ratio between the triplet and singlet excitons by facilitating the process of RISC. These emitters exhibit AIE and TADF properties, featuring quick radiative rates and low nonradiative rates. The ΦPL of these emitters reached an impressive 88%. Based on their excellent comprehensive performance, nondoped PICzPMO and PICzPMO OLEDs achieved excellent electroluminescence performance, exhibiting maximum external quantum efficiency (EQEmax) of up to 19.5%, while the doped device achieved a higher EQEmax of 20.8%. This work demonstrated that by fusing π-extended large rigid donors with different acceptors, it is possible to regulate the difference in electron-donating and electron-withdrawing abilities, resulting in a small ΔEST, high ΦPL, and fast RISC process, which is a highly feasible strategy for designing efficient TADF molecules.

Anion-directed cationic supramolecular dyes with reversible mechanochromism and fabric staining

It is vital to create supramolecular dyes with excellent photo-luminescence properties based on host-gust interaction. In this study, we present three novel self-assembled cationic supramolecular dyes driven by host-guest electrostatic interaction and with ultrasmall cavities. These cationic dyes were developed and synthesized using pyridine-substituted phenanthrene, triphenylamine (TPA), and tetraphenyl ethylene (TPE) as chromophores through the pyridine quaternary ammonium salt reaction. These anion-trapped supramolecular dyes exhibit outstanding aggregation-induced emission (AIE) characteristics as well as reversible mechanochromism behavior and high solid-state fluorescence quantum yields (∼60.87 %). Furthermore, the cationic supramolecular dyes directly stain cotton fibers with 50 % dyeing rate in water-methanol solutions, in which the deprotonated glucose-O- guest possibly interacts with the cationic dye through host-guest encapsulation. Additionally, we characterized the dyeing process through IR spectroscopy, UV–vis spectroscopy, fluorescence spectroscopy, and energy-dispersive X-ray spectroscopy (EDS). Due to the reversible, tractable, and high-contrast mechanochromism of the dyes, they can make up a color-changing flower pattern. Thus, we anticipate that these dyes will have potential applications in information security storage and anti-counterfeiting.

New pyrrolo[3,2-b]pyrroles with AIE characteristics for detection of dichloromethane and chloroform.

Three new pyrrolo[3,2-b]pyrrole derivatives containing methoxyphenyl, pyrene or tetraphenylethylene (TPE) units (compounds 1-3) have been designed, synthesized and fully characterized. The aggregation-induced emission (AIE) properties of compounds 1-3 were tested in different water fraction (fw ) of tetrahydrofuran (THF). The pyrrolo[3,2-b]pyrrole derivative 3 containing TPE units exhibited typical AIE features with an enhanced emission (∼32-fold) in the solid state versus in solution; compounds 1 and 2 exhibited an aggregation-caused quenching effect. In addition, the steric and electronic effects of the peripheral moieties on the emission behavior, both in solution and in the solid state, have been investigated. Moreover, pyrrolo[3,2-b]pyrrole 1 exhibits high sensitivity and selectivity for dichloromethane and chloroform solvents, with the system displaying a new emission peak and fast response time under ultraviolet irradiation.

Synthesis, structure, photophysical property, stability of tetraphenylethylene-based boranil, and applications in cell imaging

A new family of tetraphenylethylene-based N,O-chelated boranil complexes (TPE-BAs) with aggregation-induced emission (AIE) characteristics were developed. X-ray crystallographic analysis indicated that the terminal substituents on the aniline moiety significantly affected the intermolecular stacking mode, thereby influencing the photophysical properties. The stabilities of these compounds are closely related to the substituents on the aniline moiety. Electron-donor-substituted TPE-BA-OMe exhibited the best stability, whereas the electron-acceptor-substituted compounds exhibited poor stability. Benefitting from its AIE properties and suitable lipophilicity, TPE-BA-OMe served as an excellent fluorescent probe for the specific bioimaging of lipid droplets in living cells.

Enhancing NIR-II Imaging and Photothermal Therapy for Improved Oral Cancer Theranostics by Combining TICT and Aggregation-Induced Emission.

In the treatment process of cancers like oral cancer, it is necessary to employ extensive surgical resection to achieve cancer eradication. However, this often results in damage to crucial functions such as chewing and speaking, leading to a poorer prognosis and a reduced quality of life. To address this issue, a multifunctional theranostic agent named MBPN-T-BTD has been developed by precisely modulating the excitation state energy distribution in the radiative/nonradiative decay pathways using the characteristics of twisted intramolecular charge transfer and aggregation-induced emission. This agent outperforms clinically utilized indocyanine green (ICG) in various aspects, including the second near-infrared window (NIR-II, 1000-1700 nm) fluorescence (FL) and photothermal conversion efficiency (PCE). Its nanoparticle form (BTB NPs) can be effectively used for high-contrast delineation of lymph node mapping and tongue and floor of mouth cancers using NIR-II FL, enabling surgeons to achieve more precise and thorough tumor clearance. For tumors located in close proximity to vital organs such as the tongue, the exceptional PCE (71.96%) of BTB NPs allows for targeted photothermal ablation with minimal damage to peripheral healthy tissues. This contribution provides a safer and more effective paradigm for minimally invasive or noninvasive treatment of oral cancer, ensuring the preservation of normal organ functions and showing potential for improving the overall prognosis and quality of life for cancer patients.

Aminobenzothiazole fused tetraphenylethene AIEgen: Ag+, Hg2+ and Fe3+ sensing applications in aqueous medium

6-(1,2,2-triphenylvinyl)benzo[d]thiazol-2-amine (TPE-BTA) was synthesized using a multistep reaction strategy. The aggregation-induced emission (AIE) characteristics of TPE-BTA have been established in DMSO–water solvent mixtures. The color of the TPE-BTA solution changed from dark blue in DMSO to fluorescent blue in DMSO: water (70–95 %, v/v ratio). The receptor TPE-BTA showed sensitive sensing towards Ag+, Hg2+, and Fe3+ ions in the presence of the tested metal cations. TPE-BTA exhibited a limit of detection (LOD) towards Ag+, Hg2+, and Fe3+ ions as low as 4.96 × 10−7M, 2.00 × 10−7M, and 1.74 × 10−7M, respectively. The stoichiometry of complex formation between TPE-BTA and Ag+, Hg2+, and Fe3+ was 1:1 (TPE-BTA: Ag+, TPE-BTA: Hg2+, and TPE-BTA: Fe3+) based on fluorescence studies.

Ratiometric fluorescence determination of alkaline phosphatase activity based on carbon dots and Ce3+-crosslinked copper nanoclusters.

A new ratiometric fluorescent probe for efficient determination of ALP was developed. The probe was constructed by combining Ce3+-crosslinked copper nanoclusters (Ce3+-CuNCs) which exhibit the aggregation-induced emission (AIE) feature with carbon dots (CDs). The introduction of phosphate (Pi) induced the generation of CePO4 precipitation, resulting in significant decrease of fluorescence emission of CuNCs at 634nm. At the same time, the fluorescence of CDs at 455nm was obviously enhanced, thus generating ratiometric fluorescence response. Based on the fact that the hydrolysis of pyrophosphate (PPi) by ALP can produce Pi, the CD/Ce3+-CuNCs ratiometric probe was successfully used to determine ALP. A good linear relationship between the ratiometric value of F455/F634 and ALP concentrations ranging from 0.2 to 80 U·L- 1 was obtained, with a low detection limit of 0.1 U·L- 1. The ratiometric responses of the probe resulted in the visible fluorescence color change from orange red to blue with the increase of ALP concentration. The smartphone-based RGB recognition of the fluorescent sample images was used for ALP quantitative determination. A novel ratiometric fluorescent system based on Ce3+-CuNCs with AIE feature and CDs were constructed for efficient detection of ALP.

Creation of High-Quality Deep-Blue AIE Emitter with a Crossed Long-Short Axis Structure for Efficient and Versatile OLEDs.

Developing deep-blue emitters for organic light-emitting diodes (OLEDs) is critical but challenging, which requires a good balance between light color, exciton utilization, and photoluminescence quantum yield (PLQY) of solid film. Herein, a high-quality deep-blue emitter, abbreviated 2TriPE-CzMCN, is designed by introducing an aggregation-induced emission (AIE) group into a crossed long-short axis (CLSA) skeleton. Theoretical and experimental investigations reveal that the CLSA molecular design can achieve a balance between deep-blue emission and triplet-excitons utilization, while the high PLQY of the solid film resulting from the AIE feature helps to improve the performance of OLEDs. Consequently, when 2TriPE-CzMCN is used as the emitting dopant, the OLED exhibits a deep-blue emission at 430nm with a record-high maximum external quantum efficiency (EQE) of 8.84%. When 2TriPE-CzMCN serves as the host material, the sensitized monochrome orange and two-color white OLEDs (WOLEDs) realize high EL performances that exceed the efficiency limit of conventional fluorescent OLEDs. Moreover, high-performance three-color WOLEDs with a color rendering index (CRI) exceeding 90 and EQE up to 18.08% are achieved by using 2TriPE-CzMCN as the blue-emitting source. This work demonstrates that endowing CLSA molecule with AIE feature is an effective strategy for developing high-quality deep-blue emitters, and high-performance versatile OLEDs can be realized through rational device engineering.

The inherent AIE feature revealed the drug molecular state in cyclodextrin metal–organic framework for enhanced stability and absorption

The amorphous form of a drug can greatly improve the solubility and rates of dissolution for enhancing oral bioavailability. However, amorphous drugs tend to crystallize thus negating their solubility advantages. Here, we use a nanoconfinement strategy to prevent the crystallization of amorphous solids by loading the poorly soluble drug indomethacin (IMC) into a porous γ-cyclodextrin-based metal–organic framework (CD-MOF). The inherent aggregation-induced emission (AIE) property of IMC was successfully applied as a sensitive fluorescence imaging tool to visualize its molecular state in the solid form. A distinct high-energy, non-aggregated molecular state of IMC in CD-MOF was revealed by the AIE turn-off phenomenon together with other solid-state characterization methods. The IMC@CD-MOF exhibited excellent physical stability even when stored at high temperature or humidity. The high supersaturated drug solutions were immediately generated and maintained during the dissolution of IMC@CD-MOF, resulting in a great enhancement of in vivo bioavailability. The inherent AIE feature of drugs can facilitate the understanding of the structure–property relationship in complex delivery systems, which is essential for the design and optimization of drug carriers with desired stability and biopharmaceutical performance.

Biotin-conjugated Ru(II) complexes with AIE characteristics as mitochondria-targeted photosensitizers for enhancing photodynamic therapy by disrupting cellular redox balance

The potential use of Ru(II) complexes as photosensitizers (PSs) in photodynamic therapy (PDT) has gained significant attention. In comparison with fluorophores with aggregation-caused quenching (ACQ), fluorophores with aggregation-induced emission (AIE) characteristics exhibit sustained fluorescence and dispersibility in aqueous solutions. PSs with AIE characteristics have received much attention in recent years. Herein, we reported two novel biotin-conjugated Ru(II) polypyridyl complexes (Ru1 and Ru2) with AIE characteristics. When exposed to 460 nm (10 mW cm−2) light, Ru1 and Ru2 exhibited outstanding photostability and photocatalytic activity. Ru1 and Ru2 could efficiently generate singlet oxygen and induce pUC19 DNA photolysis when exposed to 460 nm light. Interestingly, both Ru1 and Ru2 also functioned as catalysts for NADH oxidation when exposed to 460 nm light. The presence of biotin fragments in Ru1 and Ru2 enhanced the specific uptake of these complexes by tumor cells. Both complexes showed minimal toxicity to selected cells in the dark. Nevertheless, the phototoxicity of both complexes significantly increased upon 460 nm light irradiation for 15 min. Further experiments revealed that Ru2 primarily accumulated in mitochondria and might bind to mitochondrial DNA. Under 460 nm light irradiation, Ru2 induced the generation of reactive oxygen species (ROS) and NADH depletion disrupting intracellular redox homeostasis in A549 cells, activating the mitochondrial apoptosis pathway resulting in up-regulation of apoptotic marker caspase-3, effectively damaged A549 cell DNA and arrested A549 cell cycle in the S phase. In vivo anti-tumor experiments were conducted to assess the effects of Ru2 on tumor growth in A549 tumor-bearing mice. The results showed that Ru2 effectively inhibited tumor growth under 460 nm light irradiation conditions. These findings indicate that Ru2 has great potential as a targeted photosensitizer for mitochondrial targeting imaging and photodynamic therapy of tumors.

An aggregation-induced emission-based ratiometric fluorescent chemosensor for Hg(II) and its application in Caenorhabditis elegans imaging

A chromone-based ratiometric fluorescent probe L2 was developed for the selective detection of Hg(II) in a semi-aqueous solution based on aggregation-induced emission (AIE) and chelation-enhanced fluorescence (CHEF) effect. The probe L2 fluoresced significantly at 498 nm in its aggregated state, and when chelated with Hg(II), the soluble state fluoresced 1-fold higher. In addition, Job’s plot reveals that the probe forms a 1:1 stoichiometry complex with Hg(II) with an association constant of 9.10 × 103M−1 estimated by the BH plot. The probe L2 detects Hg(II) down to 22.47 nM without interference from other interfering ions. The FTIR, ESI mass, and DFT-based computational studies investigated the binding mechanism of probe L2 with Hg(II). Taking advantage of its AIE characteristics, the probe L2 was successfully applied for bio-capability analysis in Caenorhabditis elegans (a nematode worm) imaging of Hg(II) in a living model.

Coupling nano-redox carbon dots with nontraditional AIE-polysaccharides on a smart fabric for healthcare sensing systems

Creating bio-based fluorescent probes with visual-sensing abilities and anti-infection performance is highly desirable but remains challenging. Herein, a multifunctional dual-responsive biopolymeric nanocoating has been designed with synergistically enhanced fluorescent and antibacterial properties that simply implemented by the combination of tannic acid rooted carbon dots (TN, redox-sensitive) and alginate-zinc complex (SA-Zn, ionic-sensitive) possessing the aggregation-induced emission (AIE) characteristics. The mussel-inspired catechol groups and alginate-metal aggregates afford great film-forming abilities on diverse substrates while the entrapped TN enable manipulation of the redox-dependent fluorescent and antibacterial properties via generating reactive free radicals (ROS). The concept of facile pre-sensing and treatment towards in-home sensing application has been perfectly realized on a commercial fabric wipe, demonstrating excellent detection capabilities for biological molecules (e.g., H2O2 and metal cations) and synergistically enhanced antibacterial performance. Therefore, bridging the nano-redox carbon dots with nontraditional luminescent polysaccharides can provide enormous potential into advanced fluorescent materials for emerging healthcare applications.

Reblooming of the cis-Bis(2-phenylpyridine) Platinum(II) Complex: Synthesis Updating, Aggregation-Induced Emission, Electroluminescence, and Cell Imaging.

Studies on the syntheses, photophysical properties, and applications of cis-bis(2-phenylpyridine) platinum(II) complex (Pt(ppy)2) family are of great importance, but very limited progress has been achieved to date. Herein, a one-pot method was established for the syntheses of Pt(ppy)2-type complexes Pt-ppy and Pt-tBu. These two compounds were nonemissive in dilute solutions. However, they produced intense red and deep-red phosphorescence in the aggregation and film states, with lifetimes and quantum yields up to 1.92 μs and 70%, respectively, exhibiting unique aggregation-induced emission (AIE) characteristics. According to the experimental and theoretical studies, molecular configuration transformation (MCT) in the excited state may occur because of the d-d transition from the Pt center, causing nonradiative transitions in the solution. Nevertheless, the MCT would be largely restricted by the intermolecular interactions or rigid matrix, thereby enabling efficient phosphorescence in the aggregation state and in the PMMA films. Consequently, the AIE characteristics of Pt-ppy and Pt-tBu probably result from the restriction of molecular configuration transformation (RMCT). Due to the π-π and/or weak Pt-Pt interactions and the concentration-dependent emission characteristics, they emit deep-red and NIR emissions generated by excimer and/or MMLCT emitting species. Inspired by their AIE features, electroluminescence and cell imaging applications are explored. To the best of our knowledge, this is the first comprehensive study on the synthesis optimization, photophysical properties, AIE characteristics, and applications of the Pt(ppy)2-type complexes, which may rebloom the research studies on this type of Pt(II) complex family and provide valuable insights on the development of phosphorescent AIE metal-organic complexes.

Tetraphenylethylene-based AIE nanoprobes for labeling lysosome by two-photon imaging in living cells

Lysosomes are essential cellular organelles, serving vital functions in cellular metabolism and degradation. The design of specifically targeting lysosomes probes with aggregation-induced emission (AIE) characteristics using two-photon excitation techniques is significance and challenging work. Here we designed and synthesized two tetraphenylethylene (TPE)-based AIE fluorescence probes, naming TPE-Ma and TPE-Py, with TPE as the matrix and morpholine (Ma) or pyrrolidone (Py) as the targeting group. These probes exhibit a significant Stokes shift, low cytotoxicity, two-photo fluorescence imaging and lysosome-specific targeting capability ensuring their suitability for fluorescence imaging applications. To enhance the water solubility and cellular accumulation of TPE-Ma and TPE-Py in tumor cells, we employed a biocompatible polymer 1,2-distearoyl-sn-glycero-3-phosphoethanolamine-N-[methoxy(polyethylene glycol)-2000] (DSPE-mPEG2000) as a nanocarrier. By encapsulating TPE-Ma and TPE-Py within DSPE-mPEG2000, we successfully developed two AIE fluorescent nanoprobes known as DSPE@ TPE-Ma and DSPE@ TPE-Py. The results demonstrated that fluorescent nanoprobes DSPE@ TPE-Ma and DSPE@ TPE-Py possess excellent cell permeability, biocompatibility, superior photostability and specific targeting towards lysosomes in MCF-7 cells. Our findings highlight the potential of these fluorescent nanoprobes as effective tools for two-photon fluorescence imaging and targeted detection of lysosomes in cancer cells.

A deep-red fluorophore based on naphthothiadiazole as emitter with hybridized local and charge transfer and ambipolar transporting properties for electroluminescent devices.

Herein, we report the synthesis and characterization of an efficient ambipolar charge-carrier-transporting deep-red fluorophore (TPECNz) based on a donor-acceptor-donor (D-A-D)-type molecule and its application as a non-doped emitter in an organic light-emitting diode (OLED). The fluorophore TPECNz contains naphtho[2,3-c][1,2,5]thiadiazole (Nz) as a strong acceptor unit symmetrically functionalized with N-(4-(1,2,2-triphenylvinyl)phenyl)carbazole as a donor and aggregation-induced emission (AIE) luminogen. The experimental (solvatochromic and emission in THF/water mixtures studies) and theoretical investigations prove that TPECNz retains cooperative hybridized local and charge transfer (HLCT) and weak AIE features. Thanks to its D-A-D-type structure with a proper twist angle between the D and A units, a strong electron deficiency of the Nz unit, and electron-donating and hole-transporting natures of carbazole, TPECNz exhibits a strong deep red emission (λem = 648 nm) with a high fluorescence quantum yield of 96%, outstanding thermal property (Tg = 236 °C), and ambipolar charge-carrier-transporting property with a decent balance of mobility of electrons (1.50 × 10-5 cm2 V-1 s-1) and holes (4.42 × 10-6 cm2 V-1 s-1). TPECNz is successfully employed as a non-doped emitter in an OLED which displays deep red electroluminescent emission peaked at 659 nm with CIE coordinates of (0.664, 0.335)), an EQEmax of 3.32% and exciton utilization efficiency (EUE) of 47%.

Biotin receptor and mitochondria dual targeted AIE photosensitizer for fluorescence imaging guided photodynamic anticancer therapy

Rational design of organelle targeted therapeutic platform in where the drug can be targeted to destroy tumor cells as much as possible, is one of the effective ways to improve the therapeutic outcomes and minimize the cytotoxicity to normal cells. Here, photosensitizer TSPy-B with aggregation-induced emission (AIE) feature, biotin receptor and mitochondria dual-targeted capability, and high reactive oxygen species (ROS) generation efficiency was designed for fluorescence imaging guided photodynamic therapy (PDT) by linking biotin group to D-π-A type AIE dyes via ester bonds. Notably, cell imaging experiments showed that TSPy-B could selectively target tumor cells with biotin receptor overexpression and further exhibit mitochondria targeting ability. The in vitro anticancer mechanism confirmed that after cell internalization, TSPy-B localized in the mitochondrial site and produced ROS resulting in mitochondrial dysfunction and cell death. ROS generation experiments showed that TSPy-B could simultaneously produce 1O2 and highly toxic free radicals which not depended on the oxygen level of solid tumor. The cell killing effect of TSPy-B was also confirmed in hypoxic culture model. In vivo photodynamic therapy experiments demonstrated that TSPy-B could effectively inhibit tumor growth and had good biological safety. This work provides a choice for development of highly targeted photosensitizers for clinical fluorescence imaging guided PDT.