Tumor microenvironment ameliorative and adaptive nanoparticles with photothermal-to-photodynamic switch for cancer phototherapy.

The notorious tumor microenvironment (TME) usually becomes more deteriorative during phototherapeutic progress that hampers the antitumor efficacy. To overcome this issue, we herein report the ameliorative and adaptive nanoparticles (TPASIC-PFH@PLGA NPs) that simultaneously reverse hypoxia TME and switch photoactivities from photothermal-dominated state to photodynamic-dominated state to maximize phototherapeutic effect. TPASIC-PFH@PLGA NPs are designed by incorporating oxygen-rich liquid perfluorohexane (PFH) into the intraparticle microenvironment to regulate the intramolecular motions of AIE photosensitizer TPASIC. TPASIC exhibits a unique aggregation-enhanced reactive oxygen species (ROS) generation feature. PFH incorporation affords TPASIC the initially dispersed state, thus promoting active intramolecular motions and photothermal conversion efficiency. While PFH volatilization leads to nanoparticle collapse and the formation of tight TPASIC aggregates with largely enhanced ROS generation efficiency. As a consequence, PFH incorporation not only currently promotes both photothermal and photodynamic efficacies of TPASIC and increases the intratumoral oxygen level, but also enables the smart photothermal-to-photodynamic switch to maximize the phototherapeutic performance. The integration of PFH and AIE photosensitizer eventually delivers more excellent antitumor effect over conventional phototherapeutic agents with fixed photothermal and photodynamic efficacies. This study proposes a new nanoengineering strategy to ameliorate TME and adapt the treatment modality to fit the changed TME for advanced antitumor applications.

Tailoring near-infrared amyloid-ß probes with high-affinity and low background based on CN and amphipathic regulatory strategies and in vivo imaging of AD mice.

Amyloid-ß (Aß) species (Aß fibrils and Aß plaques), as one of the typical pathological markers of Alzheimer's disease (AD), plays a crucial role in AD diagnosis. Currently, some near-infrared I (NIR I) Aß probes have been reported in AD diagnosis. However, they still face challenges such as strong background interference and the lack of effective probe design. In this study, we propose molecular design strategy that incorporates CN group and amphiphilic modulation to synthesize a series of amphiphilic NIR I Aß probes, surpassing the commercial probe ThT and ThS. Theoretical calculations indicate that these probes exhibit stronger interaction with amino acid residues in the cavities of Aß. Notably, the probes containing CN group display the ability of binding two distinct sites of Aß, which dramatically enhanced the affinity to Aß species. Furthermore, these probes exhibit minimal fluorescence in aqueous solution and offer ultra-high signal-to-noise ratio (SNR) for in vitro labeling, even in wash-free samples. Finally, the optimal probe DM-V2CN-PYC3 was utilized for in vivo imaging of AD mice, demonstrating its rapid penetration through the blood-brain barrier and labelling to Aß species. Moreover, it enabled long-term monitoring for a duration of 120 min. These results highlight the enhanced affinity and superior performance of the designed NIR I Aß probe for AD diagnosis. The molecular design strategy of CN and amphiphilic modulation presents a promising avenue for the development Aß probes with low background in vivo/in vitro imaging for Aß species.

Biomimetic androgen receptor-based AIE biosensor for detecting bisphenol analogues: An integrating in silico topological analysis, molecular docking, and experimental validation study.

Bisphenol analogues are the typical class of endocrine disrupting chemicals (EDCs) that interfere with binding of endogenous hormones to androgen receptor (AR). With the expansion of industrial activities and the intensification of environmental pollution, an increasing array of bisphenol analogues is being released into the environment and food chain. This highlights the urgency to develop sensitive methods for the detection of bisphenol analogues. Here, we propose a biomimetic AR-based biosensor platform for detecting bisphenol analogues (BPF, TBBPA, and TBBPS) by binding with Aggregation-Induced Emission (AIE) probes. Following a comparison of the PROSS and ABACUS methods, biomimetic AR was designed using the ABACUS approach and subsequently expressed in vitro via the E. coli expression system. Through molecular docking and the observation of fluorescence changes upon binding with biomimetic AR, BS-46006 was selected as the AIE probe for the biosensor. The biomimetic AR-based biosensor showed sensitive detections of BPF, TBBPA, and TBBPS within a range of 0-50 mM. To further elucidate the multi-residue recognition mechanism, molecular orbitals, Electron Localization Function (ELF), and Localized Orbital Locator (LOL) were systematically calculated in this study. Lowest unoccupied molecular orbital and highest occupied molecular orbital indicated the energy gap of BPF, TBBPA, and TBBPS, which correspond to 0.12812, 0.19689, and 0.18711 eV, respectively. ELF and LOL offered clearer perspective through heat maps to visually represent the electron delocalization in BPF, TBBPA, and TBBPS. The matrix effect analysis suggested that the responses of bisphenol analogues in soil matrices could be effectively mitigated through sample pretreatment. The analysis of spiked soil samples showed the acceptable recoveries ranged from 91 % to 105 %. Additionally, the biomimetic AR-based AIE biosensor, which combines multi-residue detection with Tolerable Daily Intakes, shows great promise for the risk assessment of bisphenol analogues. This research may present a viable approach for the analysis of environmental pollutants.

Precision Photothermal Therapy at Mild Temperature: NIR-II Imaging-Guided, H2O2-Responsive Stealth Nanobomb.

The therapeutic efficacy of photothermal therapy (PTT) under mild temperatures (<45 °C) is hindered as cancer cells can activate heat shock proteins (HSPs) to mend fever-type cellular damage swiftly. The previous attempt fabricated first-generation nanobombs (nanobomb1G) by self-assembly of polymeric NIR-II AIEgens and carbon monoxide (CO) carrier polymer mPEG(CO) to inhibit the expression of HSPs after intratumor injection. A new generation nanobomb (Stealth NanoBomb (SNB)) is developed by self-assembling small molecular NIR-II AIEgens with CO carrier polymer PLGA(CO) coated by PEG-lipid. This design allows for intravenous administration, enabling the SNB to circulate safely in the bloodstream and selectively target cancer cells. Upon accumulation in tumors, the SNB releases CO to effectively suppress HSP expression, enhancing the therapeutic efficacy of mild-temperature PTT. Compared to the previous generation, the SNB offers a safer, more stable, and more efficient CO gas/drug co-delivery system for cancer treatment. This work represents a significant advancement in PTT, providing a promising strategy for enhanced antitumor therapy with reduced systemic toxicity.

Water-soluble AIE photosensitizer in short-wave infrared region for albumin-enhanced and self-reporting phototheranostics.

Organic photosensitizers (PSs) play important roles in phototheranostics, and contribute to the fast development of precision medicine. However, water-soluble and highly emissive organic PSs, especially those emitting in the short-wave infrared region (SWIR), are still challenging. Also, it's difficult to prepare self-reporting PSs for visualizing the treatment via stimulated emission depletion (STED) nanoscopy. Thus, in this work, a water-soluble molecule of DTPAP-TBZ-I with aggregation-induced emission features is designed for the self-reporting photodynamic therapy (PDT) in an ultra-high resolution. In contrast to single molecule, its complex (DTPAP-TBZ-I@BSA) shows much enhanced fluorescence properties and reactive oxygen species (ROS) generation in SWIR window. Their photoluminescence quantum yield is determined to be ∼20.6 % and the enhancement of ROS generation is ∼18-fold. During the PDT, immigration of the complex from cytoplasm to nucleus is also observed via STED nanoscopy with a resolution of 66.11 nm, which allows self-report in the PDT treatment. DTPAP-TBZ-I@BSA is finally utilized for the imaging-guided PDT in vivo with a tumor inhibition rate of 84 %. This is the first work in albumin-enhanced water-soluble organic PSs in SWIR window for self-reporting phototheranostics at ultra-high resolutions, providing an ideal solution for the next generation of photosensitizers for precise medicine.

Solvent-induced modulation of sensitivity and selectivity in the self-assembly of tetracationic cyclophanes with cholesterol sulphate, sodium dodecyl sulfate, and sodium dodecyl benzene sulfonate: Observations of significant shifts.

Cyclophane CP-1 demonstrates markedly distinct sensitivities toward Cholesterol sulfate (CH-S), Sodium Dodecyl Sulfate (SDS), and Sodium Dodecyl Benzene Sulfonate (SDBS) when the solvent is shifted minimally from a 95 % to a 98 % HEPES-DMSO mixture. In a 98:2 HEPES-DMSO mixture, CP-1 engages in highly selective self-assembly with CH-S, which is characterized by aggregation-induced emission enhancement (AIEE) in contrast to other steroidal sulfates such as pregnenolone sulfate (PRG-S), dehydroisoandrosterone sulfate (DIAND-S), taurocholic acid (TACH-S), and the surfactants SDS and SDBS. This assembly results in an approximate 40-fold increase in fluorescence intensity with three equivalents of CH-S and allows for the detection of concentrations as low as 200 nM under physiological conditions. Dynamic light scattering (DLS) studies illustrate the aggregation of CP-1 and CH-S, with the zeta potential of each shifting from negative values to nearly zero in a 1:2 CP-1:CH-S mixture, indicating self-assembly. This aggregation behavior is reversible, as demonstrated by a corresponding decrease and then increase in fluorescence intensity with temperature variations from 25 °C to 70 °C and back to 25 °C. Scanning Electron Microscopy (SEM) and Transmission Electron Microscopy (TEM) analyses show that CP-1 forms aggregates ranging from 100 to 180 nm, which increase to 150-250 nm upon interaction with CH-S. In a 95:5 HEPES-DMSO mixture, CP-1 exhibits a stronger AIEE response with SDS and SDBS compared to CH-S. Cyclophane CP-2, when dissolved in binary DMSO-water mixtures with water content exceeding 80 %, shows similar AIEE phenomena and undergoes selective fluorescence quenching with SDS and only a 50 % increase in fluorescence intensity with CH-S, irrespective of the HEPES concentration (95 % or 98 %).

A dual-state emission luminogen for lipid droplet imaging and photodynamic therapy.

Organic luminogens with dual-state emission (DSE) have garnered widespread attention due to their versatility in the forms of both dilute solutions and solids. Despite the growing interest, most research on DSE focuses primarily on molecule design and photophysical investigation, with limited exploration of their practical applications. In this study, we introduce a novel fluorescent molecule, PCT, featuring a distinct D-π(A)-D' electronic structure. PCT exhibited efficient DSE properties, with high quantum yields in both dilute solutions (ΦTHF = 52.3 %) and solid-state (Φsolid = 74.6 %). Taking advantage of PCT's lipophilicity, we demonstrated its potential for targeted lipid droplet (LD) imaging in living cells and its utility in monitoring LD depletion during cellular starvation. To further enhance its applicability in photodynamic therapy (PDT), PCT was encapsulated within the amphiphilic triblock copolymer Pluronic F127, forming PCT@F127 nanoparticles with improved colloidal stability. These nanoparticles efficiently generated singlet oxygen (1O2) under white light irradiation, achieving a 1O2 quantum yield of 57.2 %. In vitro studies on MCF-7 cells revealed significant 1O2 generation and potent phototoxicity, leading to marked cell apoptosis and necrosis. These results underscore PCT's multifunctionality as a DSEgen, with promising applications in both bioimaging and PDT.

Visualization of the Plasmid DNA Delivery System by Complementary Fluorescence Labeling of Arginine-Rich Peptides.

Cell-penetrating peptides, such as arginine-rich peptides, encapsulate nucleic acid drugs and deliver them to intracellular compartments. Comprehensive tracking of drug delivery systems (DDSs) provides information about the behavior of the drug as well as the fate of the drug carrier after drug release, which is crucial for minimizing side effects. In this study, we labeled peptides designed to carry plasmid DNA with two types of dyes, traditional dye fluorescein and aggregation-induced emission (AIE) dye tetraphenylethylene, and subsequently tracked the DDS through the complementary ON and OFF fluorescence behaviors of the dyes. Traditional fluorescent dyes are susceptible to aggregation-caused quenching during bioimaging, a problem that is mitigated by using AIE dyes. However, by using both of these contrasting fluorescent labels, we were able to clearly visualize the DDS at different stages of its deployment, from drug transport and delivery to carrier dissociation and migration, demonstrating the feasibility of accurate DDS visualization by complementary fluorescence labeling.

Microenvironment-Activatable Probe for Precise NIR-II Monitoring and Synergistic Immunotherapy in Rheumatoid Arthritis.

Rheumatoid arthritis (RA) represents an insidious autoimmune inflammatory disorder that severely lowers the life quality by progressively destructing joint functions and eventually causing permanent disability, posing a serious public health problem. Here, an advanced theranostic probe is introduced that integrates activatable second near-infrared (NIR-II) fluorescence imaging for precise RA diagnosis with multi-pronged RA treatments. A novel molecular probe comprising a long-wavelength aggregation-induced emission unit and a manganese carbonyl cage motif is synthesized, which enables NIR-II fluorescence activation and concurrently releasing therapeutic carbon monoxide (CO) gas in inflamed joint microenvironment. This molecular probe self-assembles into a biocompatible nanoprobe, which is subsequently conjugated with anti-IL-6R antibody to afford active-targeting ability of RA. The nanoprobe exhibits significant turn-on NIR-II fluorescence signal at the RA lesion, enabling highly sensitive RA diagnosis and real-time therapeutic monitoring. The combination of ROS scavenging, on-demand CO gas release, and IL-6 signaling blockade results in potent therapeutic effect and synergistic immunomodulation impact, significantly alleviating the RA symptoms and preventing joint destruction. This research introduces a novel paradigm for the development of high-performance, activatable theranostic strategies to facilitate precise detection and enhanced treatment of RA-related diseases.

Luminescence Modulation in Boron-Cluster-Based Luminogens via Boron Isotope Effects.

Recent advances in luminescent materials highlight the significant impact of hydrogen isotope effects on improving optoelectronic properties. However, the research on the influence of the boron isotope effects on photophysical properties remains underdeveloped. This study focused on exploring the boron isotope effects in boron-cluster-based luminogens. In doing so, we designed and synthesized carborane-based luminogens containing 98% 10B and 95% 11B, respectively, and observed distinct photophysical behaviors. Compared to the 10B-enriched luminogens, the 11B-enriched counterparts can significantly enhance luminescence efficiency, prolong emission lifetime, and reduce full-width at half-maximum. Additionally, increased thermal stability, redshifted B-H vibrations, and a fourfold enhanced electrochemiluminescence intensity have also been observed. On the other hand, the biological assessments of a 10B-enriched luminogen reveals low cytotoxicity, high boron uptake, and excellent fluorescence imaging capability, indicating the potential application in boron neutron capture therapy (BNCT). This work presents the first comprehensive exploration on the boron isotope effects in boron clusters, and provides valuable insights into the rational design of organic luminogens for advanced optoelectronic and biomedical applications.

AIE-based ruthenium complexes as photosensitizers for specifically photo-inactivate gram-positive bacteria.

The emergence of multidrug-resistant bacterial have caused severe burden for public health. Particularly, Staphylococcus aureus as one of ESKAPE pathogens have induced various infectious diseases and resulted in increasing deaths. Developing new antibacterial agents is still urgent and challenging. Fortunately, in this study, based on aggregation-induced emission (AIE) ruthenium complexes were designed and synthesized, which realized the high efficiency of reactive oxygen species generation and remarkably killed S. aureus unlike conventional antibiotics action. Significantly, owing to good singlet oxygen production ability, Ru1 at only 4 µg/mL of concentration displayed good antibacterial photodynamic therapy effect upon white light irradiation and could deplete essential coenzyme NADH to disrupt intracellular redox balance. Also, the electrostatic interaction between Ru1 and bacteria enhanced the possibility of antibacterial. Under light irradiation, Ru1 could efficiently inhibit the biofilm growth and avoid the development of drug-resistant. Furthermore, Ru1 possessed excellent biocompatibility and displayed remarkable therapy effect in treating mice-wound infections in vivo. These findings indicated that AIE-based ruthenium complexes as new antibacterial agent had great potential in photodynamic therapy of bacteria and addressing the drug-resistance crisis.

Electrophoresis-driven AIE luminogens encapsulated within silica isoporous membrane for acid vapor sensing.

Acid vapors emitted by chemical industries pose an increasing threat to public health. The development of a cost-effective sensor for the on-site and real-time monitoring of environmental acid vapor is of great significance. Aggregation-induced emission (AIE) luminogens overcome the aggregation-caused quenching effect and exhibit intense fluorescence when supported in the solid matrices. Silica isoporous membrane (SIM), characterized by vertically ordered nanochannels, holds great promise as a platform for encapsulating AIE luminogens and enabling gas sensing applications. The SIM containing surfactant micelles was prepared on an ITO electrode to obtain the M-SIM/ITO, and Tetrakis(4-carboxyphenyl)ethylene (TCPE) was employed as the investigated AIE luminogen. Upon application of positive potential, the negatively charged TCPE molecules were driven into the vertically ordered nanochannels, resulting in observable AIE fluorescence. By investigating the electrophoresis conditions such as TCPE charge, nanochannel microenvironment, and driving electric field, the AIE mechanism within the nanochannels was elucidated. The fluorescence of TCPE@M-SIM/ITO exhibited high sensitivity towards acid vapor and displayed reversible changes during the absorption and desorption processes. This behavior can be attributed to the SIM's strong absorption capability towards acid vapor as well as the reversible conversion of acid vapor on TCPE aggregates. This work presented an innovative methodology for studying luminophores within an orderly nanoconfined space, leading to a new perspective on the AIE mechanism.

Modulating carbon dots from aggregation-caused quenching to aggregation-induced emission and applying them in sensing, imaging and anti-counterfeiting.

Aggregation Induced Emission Carbon Dots (AIE-CDs) address the problem of conventional CDs being quenched in the solid-state. However, there are still challenges in comprehending the luminescence mechanism. This work proposed a strategy for preparing green, yellow, and near-infrared CDs by modifying the functional groups on the precursor from hydroxyl and amino to p-methylenediamine, in which electronic supply capacity determined the redshift. Additionally, The CDs' properties transformed from Aggregation-Caused Quenching (ACQ) to AIE was realized by substituting non-rotatable hydroxyl or amino groups with the rotatable p-methylenediamine on the precursor. The resulting CDs were then applied in multifield. C-CDs was used for ratiometric detection of Al3+ and F- in pure water through three methods including fluorometer, test strip and smartphone. R-CDs was used for imaging cell nucleus and zebrafish. NIR-CDs (λem = 676 nm) exhibits dual emission, AIE and phosphorescent characteristics was used for triple anti-counterfeiting and binary information encryption. In summary, our finding presented a strategy for preparing multicolor CDs, proposed a mechanism for the transition of CDs from ACQ to AIE, and explore their multiple applications in anti-counterfeiting, information encapsulation, sensing and imaging.

Sensing the Small Change of Intermolecular Distance in Supramolecular Assembly by Using the Tunable Emission Wavelength of AIE-Active Luminogens.

The distinct molecular states - single molecule, assembly, and aggregate - of two ionic macromolecules, TPPE-APOSS and TPE-APOSS, are easily distinguishable through their tunable fluorescence emission wavelengths, which reflect variations in intermolecular distances. Both ionic macromolecules contain aggregation-induced emission (AIE) active moieties whose emission wavelengths are directly correlated to their mutual distances in solution: far away from each other as individual molecules, maintaining a tunable and relatively long distance in electrostatic interactions-controlled blackberry-type assemblies (microphase separation), or approaching van der Waals close distance in aggregates (macrophase separation). Furthermore, within the blackberry assemblies, the emission wavelength decreases monotonically with increasing assembly size, indicative of shorter intermolecular distances at nanoscale. The emission changes of TPPE-APOSS blackberry assemblies can even be visually distinguishable by eyes when their sizes and intermolecular distances are tuned. Molecular dynamics simulations further revealed that macromolecules are confined in various conformations by controllable intermolecular distances within the blackberry structure, thereby resulting in fluorescence emission with tunable wavelength.

Robust Natural Light-Absorbable and -Degradable AIE Photosensitizers for Fluorescence Labeling and Efficient Photodynamic Eradication of Algal Pollutants.

Current water pollution caused by the excessive proliferation of harmful algae urges green methods that can efficiently utilize natural light to treat algal pollution. Herein, a series of aggregation-induced emission (AIE) photosensitizers that can efficiently harness sunshine were synthesized for the environmentally friendly and biocompatible treatment of algal pollution. By tuning the number of thiophene units and the electron conjugation degree, the photosensitizers' absorptions were broadened to cover the whole visible light range. The positive charges guided photosensitizers to aggregate on algal cell surfaces, resulting in a turn-on fluorescence signal and robust reactive oxygen species generation under sunshine, thereby achieving fluorescence labeling and photodynamic eradication of algae. The eradication outcomes demonstrated that the AIE photosensitizers significantly outperformed the commercial algaecide ALG. At 20 ppm photosensitizers, 90.4% and 94.2% killing rates were achieved for C. reinhardtii and C. vulgaris, respectively, 2.8- and 3.6-fold higher than those from the same concentration of ALG. Excellent performances in inhibiting algae growth were also verified with efficiency superior to that of ALG. Importantly, the photosensitizers can self-degrade into biocompatible fragments under irradiation to avoid secondary pollution. The developed photosensitizers that possess sunshine convertibility and degradability provide an efficient tool for algal treatment, showing broad research and application prospects.

A cotton swab platform for fluorescent detection of aluminum ion in food samples based on aggregation-induced emission of carbon dots.

A novel portable cotton swab based on nitrogen-doped carbon dots (NCDs) for Al3+ detection was constructed for the first time. NCDs with bright green fluorescence were prepared by hydrothermal method with phenylhydrazine hydrochloride and 3-hydroxy-2-naphthoic acid hydrazide as precursors. The surface of NCDs was exposed to abundant functional groups (such as amino, carboxyl, hydroxyl, etc.), which was helpful for the formation of complexes between NCDs and Al3+. In the presence of Al3+, the aggregation of NCDs obviously induced their fluorescence enhancement due to the aggregation-induced emission (AIE) of NCDs. Furthermore, the quantum yield (QY) of NCDs was enhanced by 12 times with Al3+, and the fluorescence lifetime was increased by 7.54 ns. The fluorescence intensity was linearly correlated with the concentration of Al3+ (2.5-300 µM), and the limit of detection was 0.76 µM. Moreover, for the portable way, cotton swabs were successfully employed to construct the sensors for the detection of Al3+ in food samples. This proposal has potential for the application in food analysis.

Precision Delivery of Binary Cooperative Nanodrugs Self-Assembled by Berberine Glycyrrhetinic Acid Salts for Hepatocellular Carcinoma Treatment.

Berberine (BB) has demonstrated significant inhibitory effects on tumorigenesis and progression. However, its clinical application is hindered by challenges such as low bioavailability due to limited cell membrane permeability, nontargeted accumulation away from solid tumors, and increased toxicity associated with intravenous administration. To overcome these challenges, a lipophilic salt-forming strategy was employed to enhance lipophilicity, thereby promoting membrane permeability and targetability for tumor accumulation while simultaneously mitigating the toxicity associated with intravenous injection. In vitro findings revealed an almost 10-fold increase in fluorescence intensity with BB-GA NDs compared to BB alone. Furthermore, selective cytotoxicity against tumor cells exhibited a 4-fold elevation compared to normal cells. In vivo results underscored the remarkable tumor-selective accumulation of BB-GA NDs, effectively mitigating the intravenous injection toxicity associated with pure BB. The self-assembly of binary cooperative nanodrugs utilizing berberine glycyrrhetinic acid salts opens up innovative possibilities for drug delivery systems in traditional Chinese medicine.

Fluorescent Tetraphenylethylene-Based Cerium Metal-Organic Frameworks for White-Light-Emitting Diodes.

Discovery of highly efficient and thermal stable phosphors is the focus of the studies in phosphor-converted white light-emitting diodes (LEDs). Herein, a tetraphenylethylene-based cerium metal-organic framework (SYNU-2) was synthesized and characterized. The intricate architecture of SYNU-2 shows an overall 3D → 3D 2-fold interpenetration framework. SYNU-2 exhibited good luminescence properties, and its latent fingerprint developer was prepared, which showed good fluorescence and stability under ultraviolet (UV) radiation. It is worth noting that a prototype WLED device can be designed using SYNU-2 and red phosphors (Ca,Sr)AlSiN3:Eu2+ with CIE coordinates of (0.33, 0.33) at an applied 3 V bias.

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.

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.