A fluorescence "turn-on" phenomenon was observed in the β-aminoacrylate-based low-molecular-weight motif methyl-3-(propylamino)acrylate and its polymers in the presence of an acid, which catalyzes the formation of dihydropyridine derivatives. This unique feature could be applied in anti-counterfeiting patterns.
Bioorthogonal chemistry enables precise therapeutic activation trough targeted click reactions. However, the challenge of insufficient reaction kinetics in vivo and limited tumor penetration of reagents hurdles its clinical translation. We herein report a supramolecular strategy to achieve precise tumor-specific chemoimmunotherapy through ATP-responsive bioorthogonal chemistry. Pre-loading of activated alkyne derivative within a calixarene macrocycle prevents off-target reactions during circulation while enabling tumor-specific activation via ATP-mediated competitive displacement. This controlled release triggers an in situ amino-yne click reaction, simultaneously initiating targeted chemotherapy and robust immunogenic cell death (ICD). Comprehensive biological evaluations demonstrate that this host-guest complex significantly reduces systemic toxicity and enhances cellular uptake efficiency compared to the free drug. The dual targeting mechanism of combining the enhanced permeability and retention (EPR) effect with ATP responsiveness, overcomes the selectivity limitation of conventional bioorthogonal systems. The successful merger of these two fields opens new avenues for developing next-generation stimuli-responsive therapeutics with spatiotemporal control.
The transformation of a catalyst into a monomer represents a paradigm shift in synthetic design. We achieve this by mechanistically reprogramming a destructive side reaction, that is, the tertiary amine-catalyzed self-addition of activated alkynes. Introducing strong protic acids suppresses key nucleophilic intermediates, diverting the pathway toward the first metal-free amino-yne click polymerization involving tertiary amines and pyridine derivative as comonomers. Ionic poly(beta-ammonium acrylate)s (PAAs) with near-quantitative yields are obtained under ambient conditions. The PAAs exhibit clusteroluminescence, strong substrate adhesion with the strength and work of debonding for stainless steel as high as 6.4 MPa and 14,315 Nm-1, respectively, and dynamic degradability, allowing backbone reconstruction to achieve a record refractive index enhancement (Delta n = 0.194). Beyond a new polymerization, this work establishes a general strategy that leverages mechanistic understanding to repurpose reactive pathways to create innovative materials.
Background The accumulation of mitochondrial DNA (mtDNA) mutations in cells is closely linked to various human diseases. Detection of single-nucleotide variation (SNV) in mtDNA plays a crucial role in understanding the heteroplasmy of mtDNAs that contain pathogenic changes. While conventional nucleic acid sequencing-based methods are instrumental and complex, which hampered their capability in revealing the extensive diversity of mtDNA. In order to realize trace DNA analysis, recent CRISPR/Cas-based detection methods facilitated with target pre-amplification, while raised the risks of non-specific amplification and cross-carryover contamination. Thus, it is imperative to develop new methods for sensitive and precise SNV detection in mtDNA. Results This study developed a CRISPR/dCas9 (deactivated Cas9) mediated electrochemical impedimetric biosensor without target pre-amplification for sensitive and specific detection of SNVs in mtDNA. dCas9/sgRNA complexes were immobilized on the surface of indium tin oxide (ITO) electrode to specifically recognize target mtDNA sequences and initiate hybridization chain reaction (HCR) for signal amplification. Subsequently, positively charged polyethylenimine-coated silver nanoparticles (PEI-Ag NPs) were electrostatically deposited onto the HCR-generated long double-stranded DNA (dsDNA) products, leading to a marked decrease in electrochemical impedance due to the high conductivity of the nanoparticles. The concentration of mtDNA was thus quantified by monitoring the impedance change via electrochemical impedance spectroscopy (EIS). The method could distinguish single- and multi-base mismatches with a low detection limit of 67 fM without pre-amplification. It exhibits excellent anti-interference ability and excellent recovery rates of 90.0% to 108.0% in complex matrices (10% human plasma), and enables accurate mtDNA detection in cell lysates. Significance This free of pre-amplification strategy offers a highly sensitive analytical tool that enables the successfully detection of mtDNA mutation in diverse cells types, and exhibited excellent anti-interference ability in complicated biological specimen. The work presents a viable and promising strategy for the electrochemical detection of cancer-related biomarkers, indicating substantial potential in early clinical diagnosis.
Photodynamic therapy (PDT)-induced immunogenic cell death (ICD) has emerged as a promising strategy to stimulate robust antitumor immunity. However, the effectiveness of PDT-induced ICD on noncovalent photosensitizers remains suboptimal, as their oxidative capacity is influenced by limited cellular accumulation and suboptimal proximity to target tissue. In this work, we report a covalent ICD inducer, MBTP-Py, which incorporates a carbonylvinylpyridinium warhead into an aggregation-induced emission (AIE)-based photosensitizer. MBTP-Py covalently binds to amino and thiol groups on intracellular proteins with minimal cytotoxicity, thereby enhancing ROS oxidative capacity through improved cellular retention and proximity to target tissues. Upon light activation, MBTP-Py induces both ferroptosis and pyroptosis, thereby releasing damage-related molecular patterns and initiating ICD. Tumor cells treated with MBTP-Py, when used as a vaccine in animal models, significantly enhanced antitumor immune responses. Overall, this research integrates principles of covalent drugs to design a covalent ICD inducer, which promotes the development of tumor vaccines.
Short-wavelength-infrared (SWIR) organic light-emitting diodes (OLEDs) have clearly demonstrated advantageous mechanical flexibility and biocompatibility, making them potentially useful in many applications, such as bioimaging, food inspection, sensors, and human-compatible electronics. However, the performance of present pure organic semiconductors in the SWIR spectral region is hindered by their low luminescence efficiency, a phenomenon primarily attributable to strong aggregation-caused emission quenching. Here, we demonstrate the use of solution-processable aggregation-induced emission (AIE) molecules as the emitting layer for high-performance SWIR OLEDs. We tailor the exciton generation zone inside the device to achieve an improved charge balance factor and light outcoupling efficiency through the introduction of an electron-blocking layer beneath the AIE-emitting layer. The resulting device exhibits an emission peak at 1000 nm with a maximum external quantum efficiency of 0.10% and a maximum radiant exitance of 3.41 mW cm-2, representing one of the best performances among solution-processable SWIR OLEDs. Additionally, the device achieves an operational half-lifetime of 2 h at a high current density of 2200 mA cm-2 with a high initial irradiance of 2.39 mW cm-2 in ambient air, indicating stable device characteristics for practical applications. Our results establish a solid foundation for a new family of SWIR OLEDs, promising a broad range of applications.
Accurate bedside diagnosis of sepsis is essential for timely treatment and reducing mortality, yet technical limitations persist. Here, we present a multiplex-compatible lateral flow immunoassay (LFIA) that integrates a universal click-chemistry conjugation strategy with highly dispersible, film-like magnetic fluorescent probes (GFDQD@Si) to enable precise diagnosis through concurrent monitoring of pathogens and protein biomarkers. GFDQD@Si combines a two-dimensional high-area reactive interface; a magnetic interlayer for target enrichment and signal amplification; a multilayer of quantum dots for fluorescence enhancement; and an outer silica shell that suppresses background fluorescence and confers superior flowability. This architecture overcomes the size disparity between bacteria and proteins, enabling efficient cocapture of multiple proteins/bacteria and achieving faster, more sensitive detection on an LFIA platform. The platform quantitatively detects two key sepsis biomarkers─procalcitonin (PCT) and interleukin-6 (IL6)─as well as the pathogen Pseudomonas aeruginosa, with limits of detection of 4.44 pg mL-1 for PCT, 0.94 pg mL-1 for IL6, and 7 CFU mL-1 for bacteria. Validation in 75 clinical whole-blood samples demonstrated high sensitivity, ease of operation, and robustness, underscoring its potential for real-time bedside sepsis diagnosis. By simultaneously providing dual readouts of host-response biomarkers and pathogen detection, the GFDQD@Si-LFIA platform is expected to accelerate and improve clinical decision-making for sepsis.
Organic room-temperature phosphorescence (RTP) materials have rapidly emerged as a significant research area owing to their efficient triplet-state transitions, long-lived emission lifetimes, and oxygen-sensitive behavior. These features enable diverse applications in optoelectronics, biological imaging, information encryption, and anti-counterfeiting technologies. However, no review has comprehensively summarized the advances in this field. This review begins by outlining the fundamental mechanisms underlying RTP, with emphasis on intersystem crossing, triplet-state stabilization, and suppression of nonradiative decay pathways, followed by molecular design strategies for achieving efficient and long-lived RTP, particularly those involving aggregation modulation. Next, recent advances are surveyed across various material platforms, including single- and multi-component small molecules, dendrimers, polymers, supramolecular assemblies, and organic porous frameworks, in both crystalline and amorphous forms. Moreover, emerging multifunctional systems, such as clusterization-triggered phosphorescence, circularly polarized phosphorescence, and stimuli-responsive materials, are highlighted. Third, representative applications in anti-counterfeiting, sensing, bioimaging, biotherapy, and optoelectronic devices are critically examined to demonstrate the potential of RTP materials in next-generation smart systems. Finally, key challenges are addressed, including the trade-off between quantum yield and lifetime, oxygen quenching in biological environments, and the need for mechanistic insight via advanced spectroscopic and theoretical methods. In addition, future directions are proposed, such as developing color-tunable near-infrared RTP for deep-tissue imaging and integrating RTP into multifunctional device platforms.
To meet future energy demands while mitigating environmental impact, the advancement of renewable energy conversion technologies is essential. Solar cells represent the dominant technology for converting sunlight into electricity but have inherent limitations – including sensitivity to radiation damage, performance degradation at elevated temperatures, and intermittency. In this work, the potential of solar thermoelectric cells (STECs) as a complementary or alternative solar energy conversion technology is investigated. By testing STECs coated with organic photothermal materials ATT in indoor and outdoor settings, the performance of ATT-STEC was measured under various conditions, including intense sun irradiation and high temperatures. ATT-STECs saw voltage increase 120% with greater intensities from 1 to 4 suns and 170% with enhanced operating temperatures from room-temperature to 90 o C – while the commercial solar cell of the same size saw no change with increased solar irradiation and a decline in performance at high temperatures. Furthermore, under the same conditions, ATT-STEC was able to drive hydrogen production, which was not achievable by the commercial solar cell. These results indicate the unique advantages of STECs that are also the limitations of solar cells, suggesting broader potential of STECs as a complementary or alternative solar energy conversion approach in natural environments with intense sun exposure, high temperatures, and/or sizable temperature differences.
Lanthanide complexes with aggregation-induced emission(AIE)integrate the unique photo-physical properties of lanthanide ions and the AIE features,making them applicable in diverse areas.However,the progress in this area has been rarely reviewed.Herein,we summarize the advance of AIE lanthanide complexes based on the number of lanthanide centers they contain,along with the mechanism and applications in the fields of stimulus-responsive and biological imaging.Meanwhile,the current challenges and the future research directions in this area are also briefly discussed.
Cellulose-based fluorescent materials are attractive for sustainable applications owing to their biocompatibility and biodegradability; however, their practical utility is often limited by aggregation-caused quenching (ACQ) and insufficient functional diversity. Here, we report a versatile strategy to construct aggregation-induced emission (AIE)-active cellulose materials via an organobase-catalyzed hydroxyl-yne click reaction, enabling the efficient incorporation of tetraphenylethene (TPE) units into the cellulose backbone. The resulting EC-TPEs exhibit high optical transparency (>95%), full UV-shielding capability, and intense fluorescence, allowing simultaneous UV protection and real-time optical indication. Notably, the fluorescence properties can be precisely tuned by controlling the grafting ratio, enabling multicolor emission and the fabrication of high-resolution fluorescent quick response (QR) codes. Furthermore, secondary grafting of AIE-active MTPAP unit affords an acid-responsive system of EC-TPE-MTPAP with dynamic fluorescence color switching, facilitating advanced multicolor encryption and high-density information storage. Importantly, the dynamic enol ether linkages formed via the hydroxyl-yne click reaction enable an efficient amine-exchange defunctionalization process, restoring cellulose hydroxyl groups without loss of reactivity. This work establishes a reversible and modular platform for engineering multifunctional fluorescent cellulose materials, offering new opportunities for sustainable optical materials and information technologies.
Aggregation-induced emission (AIE) polymers have been extensively studied; however, the integration of AIE units into polyelectrolytes remains largely limited by the laborious multistep synthesis of pre-designed emissive monomers. Herein, we report a one-pot multicomponent polymerization method that directly produces main-chain charged polyelectrolytes with intrinsic AIE characteristics from non-emissive building blocks. By optimizing the monomer structures and reaction conditions, a series of soluble high-molecular-weight polymers with well-defined backbones were obtained in high yields. The resulting polyelectrolytes displayed robust AIE behavior, exhibiting fluorescence enhancement up to about 60-fold in an aqueous environment, and maintained excellent thermal stability. Owing to their cationic backbones, these polymers interact strongly with microbial surfaces and exhibit remarkable antimicrobial activities. This study establishes a synthetically efficient route to AIE polyelectrolytes and highlights their potential applications as multifunctional materials for bioimaging, antimicrobial therapy, and other applications.
Polyamides, as a class of high-performance polymers, have been extensively employed in critical industrial sectors. However, their further development is constrained by challenges, including harsh reaction conditions, stringent monomer purity requirements, and environmental concerns due to degradation resistance. In this work, we successfully established a catalyst-free propiolamide-based amino-yne click polymerization with 100% atom economy and outstanding regioselectivity and stereoselectivity. Polyamides with a sole E-configuration and weight-average molecular weights (M w, up to 14500) were obtained in excellent yields (up to 95%). Notably, the in situ generated enamine units from the click polymerization endow the polyamides with dynamic behavior, allowing them to be rapidly and controllably degraded upon the addition of monoamines at elevated temperature. Moreover, the incorporation of tetraphenylethylene (TPE) units endowed the resultant polyamide with aggregation-induced emission (AIE) characteristics, enabling highly specific and sensitive detection of Au3+ ions with a limit of detection of 2.101 x 10-7 M. Therefore, this work not only establishes a highly efficient catalyst-free propiolamide-based amino-yne click polymerization but also offers an innovative insight for the design and preparation of degradable and functional polyamides.
Thiol-yne click polymerization has emerged as an efficient strategy for the synthesis of functional polymers. However, catalyst-free and spontaneous thiol-yne polymerization of aliphatic thiols remains challenging because of their low ionization efficiency and poor reactivity toward conventional alkynes under ambient conditions. Herein, we report a robust and spontaneous polymerization strategy employing bis(ethynylsulfone)s monomers, in which the strongly electron-withdrawing sulfonyl group effectively activates the ethynyl groups toward nucleophilic addition by aliphatic dithiols. This transformation proceeds smoothly at room temperature without the need for catalysts or initiators, affording poly(β-thiolvinylsulfone)s (PTVSs) with high molecular weights (up to 97 300) and remarkable Z-stereoregularity (up to 97%) in excellent isolated yields (up to 97%). Density functional theory calculations support a Michael-type addition mechanism, in which sulfonyl-thiol interactions direct anti-Markovnikov addition with high Z-selectivity. This work establishes a facile, efficient, and broadly applicable synthetic platform for the construction of structurally well-defined sulfur-rich macromolecules.
Organic cathode materials based on abundant elements are promising candidates for next-generation batteries due to their structural flexibility, high theoretical capacity, and environmental friendliness. However, lithiated organic cathodes typically suffer from low redox potential and poor air stability, which limit their practical application. Herein, we demonstrate that the redox potential of lithiated organic materials can be significantly enhanced by precisely tuning the substitution pattern of functional groups. We have synthesized and investigated two isomeric lithiated tetracenequinone derivatives, lithium 5,12-dioxo-5,12-dihydrotetracene-1,4-bis(olate) (Li-2-1,4-DHTQ) and lithium 6,11-dioxo-6,11-dihydrotetracene-5,12-bis(olate) (Li-2-6,11-DHTQ), with identical chemical formulas but differing functional group configurations. Li-2-1,4-DHTQ manifested good air stability, stable cycling performance, and an average discharge plateau voltage of about 3.3 V, which was 900 mV higher than that of Li-2-6,11-DHTQ. Li-2-1,4-DHTQ exhibited an 83% capacity retention after 200 cycles at 100 mA g(-1) with a PVDF-based solid polymer electrolyte. This work provides a molecular design strategy to simultaneously achieve high voltage and air stability in organic cathodes through isomer engineering.
Ultraviolet- and violet-emitting upconversion nanoparticles (UCNPs) are promising for applications in photobiology, photochemistry, solid-state lasing, and energy storage. However, their use has been constrained by an inherently low upconversion efficiency. Here, we report that highly Er3+-doped NaYF4 UCNPs (20% Er3+) exhibit efficient ultraviolet (380 nm) and violet (410 nm) upconversion emissions under 660 nm excitation. The coating of an inert shell can effectively suppress surface quenching, further boosting their ultraviolet and violet upconversion efficiencies. We demonstrate that NaYF4:Er20%@NaYF4 enables rapid 9,10-phenanthrenequinone-electron-rich alkene (PQ-ERA) photocycloadditions even after light transmission through 2 mm of chicken tissue. Remarkably, their ultraviolet and violet outputs outperform those of conventional Tm3+-doped UCNPs. These results establish 660 nm-excited Er3+-doped UCNPs as highly efficient red-to-ultraviolet/violet luminescent probes with strong potential for deep-tissue photobiological applications.
Concealed drug abuse and delayed detection hinder global drug control efforts, necessitating rapid, on-site point-of-care detection methods. Here, we report a sensitive and practical aggregation-induced emission (AIE)-ELISA method for the quantitative detection of etomidate (ETO)—an emerging drug of abuse—in biological matrices. A water-soluble tetraphenylethylene derivative, TPE-phos, was designed and synthesized as an efficient alkaline phosphatase (ALP) substrate. In the competitive ELISA format, ALP-catalyzed hydrolysis of TPE-phos generates the poorly water-soluble TPE-OH, which spontaneously aggregates and produces strong fluorescence enhancement, enabling sensitive signal readout. The method exhibits a linear range of 0–125 ng/mL (R2 = 0.9916) and a limit of detection of 3.52 ng/mL. Satisfactory spike recoveries were obtained in artificial urine and saliva, confirming robustness in complex biological matrices. The proposed method offers a compelling balance of sensitivity, operational simplicity, and cost-effectiveness, making it a practical tool for point-of-care ETO screening in public safety and forensic contexts.
ABSTRACT Solar–thermal conversion offers a direct route for harvesting solar energy, yet most organic materials reported are limited to moderate temperatures and low‐temperature applications. Here, we report BTDyA, an organic material designed for high‐temperature solar–thermal conversion, achieved by bridging triphenylamine donors with [1,2,5]thiadiazolo[3,4‐f]benzotriazole acceptor via ethynyl linkages. BTDyA demonstrates a high molar absorption coefficient and broadband solid‐state absorption, enabled it to reach a temperature as high as 330 °C under concentrated outdoor sunlight, the highest reported value for organic solar–thermal materials. Moreover, under 1064 nm laser irradiation, the temperature could be further elevated to 377 °C. The transient absorption and photoinduced Raman spectroscopies reveal that BTDyA undergoes ultrafast nonradiative decay in the excited‐state, coupled with significant vibronic activation. These promote efficient conversion of photon energy into molecular vibronic energy and heat, while suppressing radiative losses and enhancing photothermal performance. The high‐temperature capability of BTDyA positions it as a promising candidate for solar energy harvesting and thermal storage. These findings offer critical insights into the design principles and photothermal mechanisms of organic materials for high‐temperature solar–thermal applications, paving the way for their future use in renewable energy technologies.