Stereotactic Photodynamic Therapy Using a Two-Photon AIE Photosensitizer.

Two-photon photodynamic therapy (TP-PDT) is emerging as a powerful strategy for stereotactic targeting of diseased areas, but ideal photosensitizers (PSs) are currently lacking. This work reports a smart PS with aggregation-induced emission (AIE) feature, namely DPASP, for TP-PDT with excellent performances. DPASP exhibits high affinity to mitochondria, superior photostability, large two-photon absorption cross section as well as efficient reactive oxygen species generation, enabling it to achieve photosensitization both in vitro and in vivo under two-photon excitation. Moreover, its capability of stereotactic ablation of targeted cells with high-precision is also successfully demonstrated. All these merits make DPASP a promising TP-PDT candidate for accurate ablation of abnormal tissues with minimal damages to surrounding areas in the treatment of various diseases.

Aggregation-induced emission and the working mechanism of 1-benzoyl and 1-benzyl pyrene derivatives.

Over the past decade, research studies on solid-state luminescent materials featuring aggregation-induced emission (AIE) have achieved great success. It has been proved that lots of planar ACQ (aggregation-caused quenching) chromophores can be converted to AIE luminogens (AIEgens) by combining with an AIE-active unit such as tetraphenylethene (TPE). In this work, we present a new method to create AIE luminogens just by introducing benzoyl or benzyl to a planar chromophore, pyrene. The generated 1-benzoyl and 1-benzyl pyrene derivatives exhibit weak emission when molecularly dissolved in good solvents but strong emission from pyrene dimers when aggregated in poor solvent or the solid state. Their crystal structure analysis and theoretical calculations are performed to depict the working mechanism of these new AIEgens. The results show that the structural rigidification of these 1-benzoyl pyrene derivatives is the major cause for their AIE effect. This new AIE system along with a clear working mechanism will contribute to the development of AIE-related functional materials and theories.

Spectroscopic and Theoretical Characterization of Through-Space Conjugation of Foldamers with a Tetraphenylethene Hinge.

Through-space conjugation is an important noncovalent interaction in artificial materials and biomacromolecules. Establishing relationships between geometry and property is of high significance to provide deeper insights into this phenomenon. In this work, we have focused on the through-space conjugation in a new class of foldamers with a folded tetraphenylethene core. We have studied its impact on the photophysical properties through experimental measurements and theoretical calculations. It is found that the through-space conjugation makes significant contributions to the short-wavelength absorption in these foldamers. Moreover, these foldamers exhibit aggregation-enhanced emission (AEE) and apparent blue shifts in their emission spectra on going from solution to aggregates. The structural changes are smaller in the aggregated state than those in the isolated state during the excited-state relaxation process, which results in lower re-organization energies. This accounts for the blueshifted and enhanced emissions in the aggregates.

Silole-Based Red Fluorescent Organic Dots for Bright Two-Photon Fluorescence In vitro Cell and In vivo Blood Vessel Imaging.

Robust luminescent dyes with efficient two-photon fluorescence are highly desirable for biological imaging applications, but those suitable for organic dots fabrication are still rare because of aggregation-caused quenching. In this work, a red fluorescent silole, 2,5-bis[5-(dimesitylboranyl)thiophen-2-yl]-1-methyl-1,3,4-triphenylsilole ((MesB)2 DTTPS), is synthesized and characterized. (MesB)2 DTTPS exhibits enhanced fluorescence efficiency in nanoaggregates, indicative of aggregation-enhanced emission (AEE). The organic dots fabricated by encapsulating (MesB)2 DTTPS within lipid-PEG show red fluorescence peaking at 598 nm and a high fluorescence quantum yield of 32%. Upon excitation at 820 nm, the dots show a large two-photon absorption cross section of 3.43 × 10(5) GM, which yields a two-photon action cross section of 1.09 × 10(5) GM. These (MesB)2 DTTPS dots show good biocompatibility and are successfully applied to one-photon and two-photon fluorescence imaging of MCF-7 cells and two-photon in vivo visualization of the blood vascular of mouse muscle in a high-contrast and noninvasive manner. Moreover, the 3D blood vasculature located at the mouse ear skin with a depth of over 100 µm can also be visualized clearly, providing the spatiotemporal information about the whole blood vascular network.

Multichannel conductance of folded single-molecule wires aided by through-space conjugation.

Deciphering charge transport through multichannel pathways in single-molecule junctions is of high importance to construct nanoscale electronic devices and deepen insight into biological redox processes. Herein, we report two tailor-made folded single-molecule wires featuring intramolecular π-π stacking interactions. The scanning tunneling microscope (STM) based break-junction technique and theoretical calculations show that through-bond and through-space conjugations are integrated into one single-molecule wire, allowing for two simultaneous conducting channels in a single-molecule junction. These folded molecules with stable π-π stacking interaction offer conceptual advances in single-molecule multichannel conductance, and are perfect models for conductance studies in biological systems, organic thin films, and π-stacked columnar aggregates.

2,5-difluorenyl-substituted siloles for the fabrication of high-performance yellow organic light-emitting diodes.

2,3,4,5-Tetraarylsiloles are a class of important luminogenic materials with efficient solid-state emission and excellent electron-transport capacity. However, those exhibiting outstanding electroluminescence properties are still rare. In this work, bulky 9,9-dimethylfluorenyl, 9,9-diphenylfluorenyl, and 9,9'-spirobifluorenyl substituents were introduced into the 2,5-positions of silole rings. The resulting 2,5-difluorenyl-substituted siloles are thermally stable and have low-lying LUMO energy levels. Crystallographic analysis revealed that intramolecular π-π interactions are prone to form between 9,9'-spirobifluorene units and phenyl rings at the 3,4-positions of the silole ring. In the solution state, these new siloles show weak blue and green emission bands, arising from the fluorenyl groups and silole rings with a certain extension of π conjugation, respectively. With increasing substituent volume, intramolecular rotation is decreased, and thus the emissions of the present siloles gradually improved and they showed higher fluorescence quantum yields (Φ(F) =2.5-5.4%) than 2,3,4,5-tetraphenylsiloles. They are highly emissive in solid films, with dominant green to yellow emissions and good solid-state Φ(F) values (75-88%). Efficient organic light-emitting diodes were fabricated by adopting them as host emitters and gave high luminance, current efficiency, and power efficiency of up to 44,100 cd m(-2), 18.3 cd A(-1), and 15.7 lm W(-1), respectively. Notably, a maximum external quantum efficiency of 5.5% was achieved in an optimized device.

Aggregation-induced emission and efficient solid-state fluorescence from tetraphenylethene-based N,C-chelate four-coordinate organoborons.

In it together: Thermally stable N,C-chelate four-coordinate organoborons were attained by grafting intramolecular B⋅ ⋅ ⋅N coordination into tetraphenylethene-pyridine and -quinoline adducts. They exhibit aggregation-induced emission characteristics (see figure), and high fluorescence quantum yields approaching unity in solid films.

Single-particle analysis of circulating bacterial extracellular vesicles reveals their biogenesis, changes in blood and links to intestinal barrier.

Bacterial extracellular vesicles (BEVs) are nano-size particles secreted by bacteria that carry various bioactive components. These vesicles are thought to provide a new window into the mechanisms by which bacteria affect their hosts, but their fundamental proprieties within human remain poorly understood. Here, we developed a single-vesicle analytical platform that enabled BEV detection in complex biological samples of host. Using this platform, we found the presence of BEVs in the host circulation and they were mainly derived from gut microbes. We showed that the levels of circulating BEVs in humans significantly increased with aging due to an age-related increase in intestinal permeability. Significantly different levels of BEVs in blood were also found in patients with colorectal cancer and colitis. Together, our study provides new insights into circulating BEV biology and reveals their potential as a new class of biomarkers.

Rapid and high-throughput testing of antifungal susceptibility using an AIEgen-based analytical system.

The increasing resistance among fungi to antimicrobials are posing global threats to health. Early treatment with appropriate antifungal drugs guided by the antifungal susceptibility testing (AFST) can dramatically reduce the mortality of severe fungal infections. However, the long test time (24-48 h) of the standard AFSTs cannot provide timely results due to the slow growth of the pathogen. Herein, we report a new AFST that is independent of growth rate analysis using a luminogen with aggregation-induced emission characteristics (AIEgen) named DMASP. DMASP is a water-soluble small-molecule probe that can readily penetrate the dense fungal cell wall. Based on its mitochondria-targeting ability and AIE characteristics, fungal activity can be dynamically indicated via real-time fluorescence monitoring. This allows fungal susceptibility to various antimicrobials to be assessed within 12 h in a wash-free, one-step manner. This method may serve as a promising tool to rapidly detect possible drug-resistant fungal strain and guide the precise use of antimicrobial against fungal diseases.

Point-of-Care Urinalysis with One Drop of Sample Using an Aggregation-Induced Emission Luminogen under the Coffee-Ring Effect.

Development of a practical point-of-care test for urinalysis is crucial for early diagnosis and treatment of chronic kidney disease (CKD). However, the classical gold standard detection method depends on sophisticated instruments and complicated procedures, impeding them from being utilized in resource-limited settings and daily screening. Herein, we report a rapid point-of-care device for the simultaneous quantification of microalbuminuria and leukocyte using one drop of urine. A luminogen (TTVP) with an aggregation-induced emission property can selectively activate its near-infrared fluorescence in the presence of albumin and leukocyte via hydrophobic or electrostatic interactions. The fluorescence signals from urine albumin and leukocyte could be well-separated combined with the coffee-ring effect. Using a smartphone-based detection device, simultaneous quantification of urine albumin and leukocyte was successfully achieved, which only took 20 min and required one drop of urine. The performance of this system is also verified with 120 clinical samples, which might serve as a simple, low-cost, and rapid tool for CKD screening and disease monitoring at the point of care.

Identification and Single-Cell Analysis of Viable Circulating Tumor Cells by a Mitochondrion-Specific AIE Bioprobe.

Liquid biopsies of cancer via single-cell molecular profiling of circulating tumor cells (CTCs) are hampered by the lack of ideal CTC markers. In this study, it is reported that TPN, a bioprobe with aggregation-induced emission (AIE) activity is capable of distinguishing various tumor cells from blood leukocytes based on the difference in cell mitochondria. TPN is a cell-permeant live-cell stain that has little effect on cell viability and integrity, enabling single-cell DNA/RNA analysis with improved efficiency compared with traditional antibody-based methods. Using TPN labeling, CTCs and CTC cluster are detected in the blood from patients with lung or liver cancer. The capability of TPN to identify rare tumor cells in the malignant pleural effusion samples is also demonstrated. Furthermore, RNA sequencing of single lung CTC identified by TPN is successfully performed. The findings presented here provide an antibody-free, low-cost, and nondisruptive approach for detection and genomic characterization of viable tumor cells based on a mitochondria-targeting AIE luminogen. It might serve as a new tool for monitoring of genomics dynamic of tumor and unraveling the mechanisms of tumor metastasis.

Unveiling the Different Emission Behavior of Polytriazoles Constructed from Pyrazine-Based AIE Monomers by Click Polymerization.

Polymers with aggregation-induced emission (AIE) characteristics have aroused tremendous interest because of their potential applications in large-area flexible display and luminescent self-assembling, and as stimuli-responsive and porous materials. However, the design of AIE-active polymers is always not as easy as that of small molecules because their properties are hard to predict. In some cases, the polymers prepared from the AIE-active monomers show the aggregation-caused quenching (ACQ) instead of AIE effect. To understand the structure-property relationship of the polymers constructed from the AIE monomers, in this paper, two pyrazine-containing AIE monomers were utilized to construct luminescent polymers by click polymerization. The photophysical property investigation indicates that the polytriazole containing tetraphenylpyrazine units is AIE-active, whereas that bearing 2,3-dicyano-5,6-diphenylpyrazine units suffers from the ACQ effect. Through systematical investigation, the cause for such difference was unveiled. Thus, this work provides a useful guidance for further design of AIE-active polymers.

Synthesis, aggregation-enhanced emission, polymorphism and piezochromism of TPE-cored foldamers with through-space conjugation.

A series of new folded tetraphenylethene derivatives with different substituents are stereoselectively synthesized, which exhibit interesting through-space conjugation, aggregation-enhanced emission, polymorphism and piezochromism properties.

Aggregation-induced emission of siloles.

Aggregation-induced emission (AIE) is a unique and significant photophysical phenomenon that differs greatly from the commonly acknowledged aggregation-caused emission quenching observed for many π-conjugated planar chromophores. The mechanistic decipherment of the AIE phenomenon is of high importance for the advance of new AIE systems and exploitation of their potential applications. Propeller-like 2,3,4,5-tetraphenylsiloles are archetypal AIE-active luminogens, and have been adopted as a core part in the design of numerous luminescent materials with diverse functionalities. In this review article, we elucidate the impacts of substituents on the AIE activity and shed light on the structure-property relationship of siloles, with the aim of promoting the judicious design of AIE-active functional materials in the future. Recent representative advances of new silole-based functional materials and their potential applications are reviewed as well.

High Fluorescence Efficiencies and Large Stokes Shifts of Folded Fluorophores Consisting of a Pair of Alkenyl-Tethered, π-Stacked Oligo-p-phenylenes.

A series of pure hydrocarbon fluorophores containing a pair of π-stacked oligo-p-phenylenes have been synthesized and analyzed by NMR and X-ray crystallography. They show good fluorescence in solutions and enhanced fluorescence in the aggregated state. Large Stokes shifts (up to 214 nm) have been achieved in these folded fluorophores in virtue of intramolecular energy transfer, and balanced structural rigidity and flexibility. These folded fluorophores provide perfect models for understanding the energy and charge transfer process in π-stacked systems.

Biocompatible Green and Red Fluorescent Organic Dots with Remarkably Large Two-Photon Action Cross Sections for Targeted Cellular Imaging and Real-Time Intravital Blood Vascular Visualization.

Fluorescent organic dots are emerging as promising bioimaging reagents because of their high brightness, good photostability, excellent biocompatibility, and facile surface functionalization. Organic dots with large two-photon absorption (TPA) cross sections are highly desired for two-photon fluorescence microscopy. In this work, we report two biocompatible and photostable organic dots fabricated by encapsulating tetraphenylethene derivatives within DSPE-PEG matrix. The two organic dots show absorption maxima at 425 and 483 nm and emit green and red fluorescence at 560 and 645 nm, with high fluorescence quantum yields of 64% and 22%, respectively. Both organic dots exhibit excellent TPA property in the range of 800-960 nm, affording upon excitation at 820 nm remarkably large TPA cross sections of 1.2×10(6) and 2.5×10(6) GM on the basis of dot concentration. The bare fluorophores and their organic dots are biocompatible and have been used to stain living cells for one- and two-photon fluorescence bioimagings. The cRGD-modified organic dots can selectively target integrin αvß3 overexpressing breast cancer cells for targeted imaging. The organic dots are also applied for real-time two-photon fluorescence in vivo visualization of the blood vasculature of mouse ear, providing the spatiotemporal information about the whole blood vascular network. These results demonstrate that the present fluorescent organic dots are promising candidates for living cell and tissue imaging.

Stereoselective synthesis of folded luminogens with arene-arene stacking interactions and aggregation-enhanced emission.

Tetraphenylethene derivatives with a folded Z-conformation and aggregation-enhanced emission characteristics are synthesized from 2-arylbenzophenones. The intramolecular rotation of the folded luminogens is partially suppressed, resulting in improved emission efficiencies in solutions.

Synthesis, structure, photoluminescence, and electroluminescence of siloles that contain planar fluorescent chromophores.

Herein, a new series of siloles that were 2,5-substituted with planar fluorescent chromophores (PFCs), including fluorene, fluoranthene, naphthalene, pyrene, and anthracene, were synthesized and characterized. These compounds showed weak emission in the solution state, owing to active intramolecular rotation (IMR), but the synergistic effect from electronic coupling between the PFC and the silole ring compensated for the emission quenching by the IMR process to some extent, thereby affording higher emission efficiencies than those of 2,3,4,5-tetraphenylsiloles in solution. These new siloles showed enhanced emission efficiencies in the aggregated state. The electroluminescence (EL) color and efficiency of new siloles were sensitive towards the PFC. Siloles containing naphthalene moieties showed green EL emission, whilst those containing anthracene moieties showed orange EL emission. The siloles containing pyrene moieties exhibited yellow EL emission at 546 nm, with a peak luminance of 49000 cd cm(-2) and a high current efficiency of 9.1 cd A(-1).

Efficient electroluminescence from excimers of 1,3,6,8-tetrakis(3,5-dimethylphenyl)pyrene.

Excimers are generally considered as detrimental to OLEDs. For pyrene-based chromophores, however, this is not always true. In this contribution, two new methylated tetraphenylpyrenes, 1,3,6,8-tetra-o-tolylpyrene (TTPy) and 1,3,6,8-tetrakis(3,5-dimethylphenyl)pyrene (TDMPPy), were synthesized through Suzuki coupling reactions. TDMPPy absorbs and emits light at longer wavelengths than TTPy due to its more planar conformation and thus better conjugation. TDMPPy is prone to excimer formation, thus leading to a strong bathochromic shift (84 nm) in the photoluminescence spectrum of its film. TDMPPy exhibits efficient electroluminescence originating from pyrene excimers, affording a maximum luminance of 26,670 cd m(-2) and a current efficiency as high as 10.8 cd A(-1) in a non-doped OLED (ITO/PEDOT:PSS (50 nm)/NPB (30 nm)/TDMPPy (30 nm)/TPBI (40 nm)/Ca:Ag).

Aggregation-enhanced emission and efficient electroluminescence of tetraphenylethene-cored luminogens.

A new design of luminescent materials by decorating a tetraphenylethene core with four aromatic chromophores is proposed. The generated luminogens exhibit aggregation-enhanced emission and excellent solid-state fluorescence efficiency (93-99%). Efficient non-doped OLEDs based on them afford remarkable efficiencies up to 11 cd A(-1).