Generating circularly polarized electrochemiluminescence (CP-ECL) from purely organic emitters is a significant challenge, requiring molecules that not only are chiral and luminescent but also retain their structural integrity and chiroptical properties within radical ion states. Here, we demonstrate the successful translation of a CPL-active, axially chiral scaffold to the domain of ECL. We investigate a binaphthyl core tetrasubstituted with pyrene units (R/S-B4p) and show that it forms stable radical anions that preserve the ground state's axial chirality, a prerequisite for CP-ECL that was previously undemonstrated for this class of molecules. This structural robustness allows for efficient electrochemical generation of a chiral excimer, resulting in intense mirror-image CP-ECL signals (λmax = 555 nm) with an exceptional electrochemiluminescence dissymmetry factor (|gECL|) of 1.2 × 10-2. Density functional theory calculations reveal that the binaphthyl core remains conformationally locked upon reduction. By directly comparing with a bis-substituted analogue (B2p) that fails to generate excimer ECL, we confirm the design rationale. The obtained R/S-B4p platform achieved the enantioselective sensing of chiral 2-amino-2'-hydroxy-1,1'-binaphthyl (NOBIN). This work validates rigid axial chirality as a robust strategy for organic CP-ECL, establishing a high-performance platform for advanced chiroptical sensing and background-free enantioselective analysis.
As the principal organ for the metabolism and detoxification of both exogenous and endogenous substances, the liver demonstrates heightened vulnerability to the onset of hepatic pathologies. Aberrant viscosity, acting as a potential biomarker, exhibits a significant correlation with liver diseases such as fatty liver, hepatic fibrosis, and liver injury. Therefore, real-time monitoring of viscosity fluctuations in animal models of liver disease is essential for related pathological investigations. Here, we report a novel viscosity-sensitive fluorescent probe (DJXP) with NIR excitation at 736 nm and emission at 809 nm, characterized by a large Stokes shift (67 nm), a broad operational pH range, high selectivity and excellent biocompatibility. DJXP enabled the visualization of viscosity changes in ICR mice induced by the antifungal drug nystatin, as determined by fluorescence imaging analysis. Furthermore, DJXP was employed to monitor elevated viscosity in mouse models of both lipopolysaccharide (LPS)-induced inflammation and rotenone-induced acute hepatic injury, demonstrating promising potential for the non-invasive detection and diagnosis of hepatic pathologies associated with altered viscosity.
Microplastics (MPs) and heavy metals are widespread environmental contaminants. Their co-exposure may pose greater risks to plants than either pollutant alone. Since their toxicity depends on tissue-specific distribution, precise imaging of both in plant tissues is critical for uncovering toxicity mechanisms. In this study, we used LA-ICP-MS imaging to investigate the effects of irregular polyethylene terephthalate (PET) MPs of ca. 200 nm labeled by europium chelate, spherical polystyrene (PS) MPs and cadmium (Cd), on cucumber seedlings. Following hydroponic exposure to 20 mg/L MPs, or in combination with 0.05 or 0.5 mg/L Cd for 5 days, imaging revealed preferential accumulation of MPs at leaf margins, while Cd distributed uniformly along vascular bundles. High-Cd levels promoted microplastic translocation to shoots, with an 87% increase for PS and 47% for PET, whereas co-exposure reduced net Cd accumulation in leaves by 71-76%. Irregular PET exhibited greater tissue accumulation and stronger synergism with Cd than spherical PS. All treatments decreased leaf area and chlorophyll content, with the greatest reductions under co-exposure: leaf area declined by 40% and chlorophyll content by 55%, while root length and stem height remained unchanged. Metabolomics identified persistent glutathione depletion as the primary oxidative stress indicator, accompanied by treatment-specific reprogramming of carbon metabolism, amino acid biosynthesis, and phenylpropanoid pathways. These findings demonstrated that microplastic morphology is a critical determinant of phytotoxicity and microplastic-metal synergism, with direct implications for environmental risk assessment of realistic plastic contaminants in food crop systems.
Abstract N‐propyl ether (DPE) is produced via acid‐catalyzed dehydration of n‐propanol (NPA), forming a minimum‐boiling azeotrope. Conventional separation processes face challenges in both efficiency and product purity. In this work, a multi‐scale approach was employed to develop an ionic liquids (ILs)‐based extractive separation process. Following a systematic framework from molecular structure and solvent screening to experimental validation, microscopic mechanism and process simulation, a green, efficient, and clean method for separating azeotrope using ILs was investigated. An initial screening of 378 ILs was conducted based on the COSMO‐RS model, and machine learning algorithms were introduced to achieve high‐throughput prediction of ILs viscosity. Selected ILs were evaluated for thermal stability and toxicity, confirmed by phase equilibrium experiments. Molecular simulation revealed extraction mechanisms at molecular‐electronic levels. Compared to conventional processes, the designed extraction process reduces TAC by 38.35% and cooling water consumption by 38.68%, offering a transferable strategy for the separation of alcohol‐ether azeotropes.
To address the impaired healing of diabetic wounds driven by the overproduction of peroxynitrite (ONOO-), we developed HD-ONOO, a near-infrared (NIR) activatable fluorescent probe based on a hemicyanine scaffold. The probe utilizes an ONOO--triggered degradation of a boronic acid pinacol ester moiety to initiate an intramolecular charge transfer (ICT) process, resulting in a robust fluorescence "turn-on" response at 750 nm. HDONOO exhibits exceptional selectivity and high sensitivity, with a calculated limit of detection (LOD) of 0.02 mu M. Beyond monitoring endogenous ONOO- fluctuations in RAW264.7 cells, the probe enabled high-contrast visualization and spatiotemporal quantification of ONOO- concentration in both the serum and cutaneous wound beds of diabetic mice. Furthermore, the probe successfully tracked the attenuation of ONOO- levels following metformin (MET) administration, highlighting its utility for evaluating therapeutic efficacy. Collectively, this research establishes HD-ONOO as a versatile molecular imaging tool for the early diagnosis, precision monitoring, and therapeutic assessment of diabetes-associated inflammatory complications.
Background Cancer-associated fibroblasts (CAFs) play a key role in prostate cancer (PCa) progression, though their heterogeneity and specific protumorigenic subsets remain poorly characterized. This study aimed to identify and validate a distinct THY1⁺ CAF subset associated with aggressive PCa. Methods Multiomics data from public (TCGA-PRAD, GEO) and prospective (FUSCC, n = 84) cohorts were analyzed. An 8-gene CAF-derived prognostic signature was constructed using LASSO Cox regression. THY1⁺ CAF clusters were identified via scRNA-seq. Primary CAFs were isolated from patient tissues, and THY1⁺/THY1⁻ subpopulations were purified via MACS/FACS. Angiogenic function and secretory profiles were assessed through tube formation assays, ELISA, and antibody arrays. THY1 knockdown and CXCR2 inhibition were used for mechanistic studies. Clinical relevance was evaluated via qPCR and multiplex immunohistochemistry on tissue microarrays. Results High CAF abundance correlated with aggressive clinicopathological features and poor prognosis in PCa. The 8-gene signature effectively predicted biochemical recurrence (BCR). scRNA-seq revealed THY1⁺ CAFs as a proangiogenic subpopulation. THY1⁺ CAFs enhanced angiogenesis via increased secretion of CXCL6 and VEGFA. CXCL6 promoted endothelial tube formation through CXCR2 activation, while THY1 knockdown downregulated VEGFA and impaired angiogenesis. High THY1⁺ CAF infiltration was associated with significantly worse recurrence-free survival. Conclusion THY1⁺ CAFs represent a proangiogenic subset that drives PCa progression via the CXCL6/CXCR2 axis and THY1-mediated VEGFA expression. These findings highlight stromal THY1 and the CXCL6/CXCR2 pathway as potential therapeutic targets.
A novel dual-responsive fluorescence probe, 2-[(1E)-2-[(6-dimethylthiocarbamoylnaphthalen)-2-yl]-ethenyl]-3-ethylbenzothiazolium iodide (TNB) has been developed for the discriminative sensing of viscosity and hypochlorous acid (HClO). Under high-viscous conditions, TNB's green fluorescence at 506 nm was switched on due to the inhibition of intramolecular bond rotation. Whereas in PBS aqueous buffer, the release of thiocarbamate moiety from TNB triggered by HClO forms a phenolic compound (NB-OH), which was chlorinated by excessive HClO to the final product (NB-Cl-OH) with near-infrared emission at 676 nm. Consequently, TNB enables the dual-colour visualization of viscosity or HClO fluctuations, showcasing good selectivity and photo-stability, high sensitivity, and quick response to HClO (∼ 4 s). Moreover, the fluorescence of NB-Cl-OH is highly responsive to viscosity changes, achieving dynamic monitoring of HClO and viscosity simultaneously. Possessing mitochondria-targeting capability, TNB realizes the dual-channel imaging of viscosity/HClO alterations in the process of oxidative stress and inflammation in live cells and zebrafish.
The development of novel multifunctional carbon quantum dots with red fluorescence emission is attractive and challenging for biological applications. In this study, amidinothiourea (ASU), neutral red (NR) and 3-aminophe-nylboronic acid (M-APBA) were employed as precursors. Nitrogen-doped boric acid groups-functionalized red emitting carbon quantum dots (N/B-RCDs) were synthesized through a one-step hydrothermal method. The prepared N/B-RCDs exhibited excellent aqueous solubility and stability. Through nitrogen doping, the red light emission with a maximum emission wavelength of 630 nm and a high fluorescence quantum yield of 44.58 % were achieved, which could effectively avoid interference from spontaneous short-wavelength fluorescence of tissues in biological detection applications. The N/B-RCDs could enable fluorescent detection of L-arginine (L-Arg) with a linear response range of 0-60 mu M and a detection limit as low as 0.217 mu M. Meanwhile, its fluorescence intensity showed significant pH-dependent behaviour (pH 6-8), which could be utilized for pH monitoring in the microenvironment of bacterial infection diseases. Furthermore, due to the ability of the boric acid groups on the surface of N/B-RCDs to covalently bind to cis-diols in the bacterial cell walls, N/B-RCDs showed potent antibacterial activity against Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus), with a minimum bactericidal concentration (MBC) of 1.65 mg/mL and 2.07 mg/mL, respectively. Simultaneously, N/B-RCDs could be successfully applied to bacterial fluorescence imaging to achieve real-time visual monitoring of antibacterial effects. This study provides a novel approach for developing intelligent antibacterial materials with real-time feedback function and diagnostic-therapeutic integration by constructing multifunctional red fluorescent carbon quantum dots.
Solid-state photochromic materials frequently encounter aggregation-caused quenching (ACQ) and limited functionality within flexible matrices, significantly restricting their implementation in complex logic operations. Herein, we report a synergistic molecular design strategy integrating extended conjugation and precise substituent engineering to develop complementary positive and negative photochromic spiropyrans (A-MC/B-SP) featuring bulky triphenylamine (TPA) modifications. Incorporating the TPA unit establishes a robust donor-acceptor conjugated architecture that optimizes intramolecular charge transfer. The rigid propeller conformation of TPA prevents tight intermolecular it-it stacking and provides the necessary micro-free volume for solidstate isomerization, effectively suppressing ACQ. Furthermore, terminal substituent engineering (sulfonate vs. ester groups) modulates the relative thermodynamic stability of the isomers, enabling both rare negative photochromism and conventional positive photochromism. The sulfonate derivative dispersed in a poly(methyl methacrylate) matrix achieved high-contrast, rewritable transient optical information storage. Additionally, a dynamic smart pattern fabricated on cotton textiles using both photochromic molecules demonstrated excellent solid-state fatigue resistance over multiple operational cycles. This structural configuration delivers multi-mode information encryption governed by independent dual-wavelength illumination. This comprehensive study presents a robust molecular design paradigm for advanced smart photoresponsive flexible devices.
Based on the hemicyanine fluorescent dye scaffold, a novel hydrazine-sensitive luminescent probe, CY-Br, was developed by introducing a 4-bromobutyric acid functional moiety as the responsive group. The nucleophilic attack of hydrazine triggers the elimination of the 4-bromobutyrate group from CY-Br to yield the corresponding phenol product (CY-OH), thereby promoting the intramolecular charge transfer (ICT) process and consequently giving rise to pronounced optical signal alterations (red-shifted UV absorption spectrum and amplified fluorescence emission). CY-Br demonstrates several notable advantages, comprising near-infrared luminescence at 730 nm, a fast response time of 40 s, superior selectivity and sensitivity (detection limit of 16.2 nM), as well as precise mitochondria targeting capability. The response mechanism was investigated employing nuclear magnetic titration and mass spectrometry techniques, with subsequent validation through theoretical computational analysis. CY-Br-coated paper strips were developed as a portable and efficient sensing platform for hydrazine detection. Furthermore, CY-Br exhibited remarkable efficacy in fluorescence imaging of both exogenous and endogenous hydrazine in live cellular and zebrafish models. By employing CY-Br, the in situ visualization of drug-induced hydrazine release within live cells and zebrafish has been achieved.
Precise control of excited-state dynamics is essential for advancing molecular materials. Herein, we present a supramolecular strategy utilizing mechanical interlocking to regulate photophysical pathways and molecular recognition. Three rotaxanes were synthesized by positioning a dibenzo-24-crown-8 macrocycle at specific sites along a naphthalimide-based axle. Femtosecond transient absorption spectroscopy revealed that the relaxation of the excited-state is critically governed by the spatial separation: the closer the macrocycle to the fluorophore, the slower the twisted intramolecular charge transfer process. Single-crystals of the rotaxane showed a lamellar architecture, where the macrocycle acts as a pre-organized gatekeeper for the fluorophore. Therefore, highly sensitive and selective detection of methanol vapor is realized based on the rotaxane film. In addition, a portable sensor for reliable (limit of detection: 0.099% vol.), rapid (<3 s), and reusable methanol detection in adulterated beverages is achieved. Our work establishes mechanical interlocking as a versatile approach to excited-state manipulating and sensor design.
With the expansion of TiO2 applications in various fields, TiO2 inevitably enters the soil, increasing the possibility of plant roots being exposed to high concentrations of TiO2. Therefore, it is important to study plant growth under TiO2 exposure conditions. In this study, the combination method of inductively coupled plasma emission spectroscopy (ICP-OES) and laser ablation inductively coupled plasma mass spectroscopy (LA-ICP-MS) was used to evaluate the effect of TiO2 on the content and distribution of nutrient elements in different parts of cucumber seedlings. The results showed that the low concentrations (50 mg/L, 100 mg/L and 200 mg/L) of TiO2 had gradually enhanced the growth of cucumber seedlings, while the high concentration (500 mg/L) of TiO2 had a significant inhibitory effect on the plant. The contents of elements (Ti, K, Ca, Mg, Mn, Fe, Zn, and Cu) in cucumber seedling roots, stems and leaves incubated with 200 mg/L TiO2 were determined by ICP-OES, and the results showed that the uptake of TiO2 increased the content of nutrient elements in the plant. High-resolution imaging of Ti, Ca, Mg, Mn, Fe, Zn, and Cu in roots, stems, and leaves using LA-ICP-MS showed that Ti accumulated mainly at the margins of the leaves. Ca, Mg, Mn, Fe, Zn, and Cu in the leaves were mainly concentrated in the main veins and lateral veins. By evaluating the content and distribution of elements in the plant with ICP-OES and LA-ICP-MS, it provides a new idea to study the mechanism of nanoparticles in the plant. It provides a theoretical basis for the correct use of nanomaterials, which is of great significance in promoting the sustainable development of agriculture.
A new mitochondria-targeting fluorescent probe, 2-[(1E)-2-[(6-(dimethylamino)naphthalen)-2-yl]-ethenyl]-3-benzylbenzothiazolium bromide (NB), capable of simultaneously detecting viscosity and hydrogen sulfite ion (HSO₃-), was synthesized. Under conditions of high viscosity, the near-infrared emission (710 nm) of NB was switched on as a result of the restriction of intramolecular bond rotation. In Phosphate Buffered Saline (PBS) aqueous solution, the Michael addition of HSO₃- to probe NB perturbs its π-conjugated system, inducing a fluorescence quenching at 710 nm accompanied by concurrent fluorescence enhancement at 424 nm, thereby enabling ratiometric detection of HSO₃-. Consequently, NB enables dual-wavelength fluorescence visualization of viscosity/HSO3- alterations, demonstrating superior selectivity, good sensitivity and photo-stability. Probe NB has been applied to determine the bisulfite in food matrices, demonstrating acceptable recovery rates (95.40% - 106.2%) and excellent method precision (RSD < 3%). Additionally, NB has demonstrated utility in dual-channel imaging for visualizing fluctuations in pathologically relevant viscosity and HSO3- concentrations in both live cells and zebrafish models. The probe is capable of differentiating cancerous and common cells through viscosity monitoring. Notably, NB can monitor the level fluctuation of endogenous SO2 during acetaminophen-induced hepatic injury, establishing its good potential for investigating SO₂-mediated physiological and pathophysiological processes.
Excessive intracellular accumulation of metal ions results in metal-dependent programmed cell death, including ferroptosis and cuproptosis. However, cancer cells have defences against these processes, which allow them to resist therapy. Therefore, this work reports a laser-controlled cascade bioreactor based on gold and silica-coated Cu- and Mn-doped iron oxide nanocrystals (IONCs) loaded with the drug disulfiram (DSF). The resultant DSF/IONC@Au/MSN-TA nanoparticles (NPs) can deliver synergistic tumor metalloimmunotherapy through ferroptosis and cuproptosis. Under near-infrared laser (NIR) irradiation, DSF is released and chelates with Cu2+ to form Cu+ species in cancer cells, which leads to mitochondrial dysfunction via cuproptosis. The presence of gold nanodots on the DSF/IONC@Au/MSN-TA NPs allows them to consume intracellular glucose and sensitize cancer cells to cuproptosis. The DSF/IONC@Au/MSN-TA NPs induce ferroptosis via waterfall-like cyclic catalytic reactions, and iron ions released by the NPs consume glutathione (GSH), thereby enhancing sensitivity to cuproptosis and ferroptosis. The presence of manganese ions augments the efficacy of these processes and additionally allows imaging to be performed. A detailed physicochemical characterization of the NPs is reported, along with a series of assays to study the mechanisms of their biocatalytic activity. The NPs' biocompatibility is also established, and they are found to be appropriate for bioimaging and theranostic applications. Our work thus offers an innovative route for targeted tumor metalloimmunotherapy.
A dielectric barrier discharge microplasma atomic emission spectrometry-cryogenic imaging platform (DBDAESCI) was constructed for rapid element imaging in biological samples. The platform has a simple configuration by using quartz plates as sample stage and dielectric layer between two electrodes to facilitate direct excitation of elements by the dielectric barrier discharge (DBD) microplasma under ambient pressure. It couples a homemade cryogenic sample stage which ensures that no water loss during the imaging process, which is advantageous for optimal sample excitation and consequently enhances signal intensity. In addition, it avoids the destruction of biological sample caused by the discharge energy, which ultimately maintains the native morphology of the biological specimens. The platform provides a detection limit of 6.5 mu g g-1 for Na, with a relative standard deviation of 3.0 % (n = 250) for the imaging of 100 mu g g-1 Na in biological sample. Carrot samples were analyzed at a spatial resolution of 100 mu m, and the imaging capability was successfully demonstrated at cryogenic conditions. It indicates that the DBD-AESCI provides a low-power, portable, and cost-effective atmospheric pressure imaging technology, which exhibits great potential for rapid on-site bio-imaging applications
Hydroquinone (HQ) and catechol (CC) are isomers of dihydroxybenzene that are commonly found in various chemical applications. Due to their considerable toxicity, they are recognized as significant organic pollutants in the environment. Therefore, developing efficient HQ and CC detection methods is particularly important. While nanozyme research has gained significant attention, creating nanozymes with high specificity continues to be a major challenge. Here, this study report that the copper-doped carbon dots (Cu-CDs) nanozyme exhibits excellent laccase-like activity and can specifically catalyze the oxidation of HQ and its isomer CC, without catalyzing the oxidation of resorcinol and other common laccase substrates (2,4-dichlorophenol, etc.). In addition, a highly selective detection platform for hydroquinone and catechol using Cu-CDs nanozyme was established. The test platform was further prepared into a portable test swab. With the help of a smartphone, the test swab showed good sensitivity and anti-interference capability, and the detection limits of HQ and CC were 0.695 and 0.016 mu M, respectively. Also, the reaction pathway and potential specific catalytic mechanism of Cu-CDs were proposed based on density functional theory (DFT) calculation. This study could aid in advancing portable sensors and enable the precise detection of phenolic compounds in intricate samples.
Chiral supramolecular organic frameworks (SOFs) and hydrogen-bonded organic frameworks (HOFs) remain an unexplored field, with very few reported examples. Here, three chiral SOFs with perfect two-dimensional (2D) framework structures are constructed by self-assembly between the chiral macrocyclic host molecule and different guest molecules through host-guest and hydrogen-bonding interactions. Variations in the guest structures lead to different host-guest interactions. The formation of the 2D frameworks of the chiral host and the guest molecules realizes chirality transfer and enhances the performance of circularly polarized luminescence (CPL) through strong charge transfer (CT) mechanisms, leading to the successful regulation of the CPL of the obtained SOF series. Chiral SOFs are significant enough due to their ability to combine chirality with versatile porous frameworks, leading to innovative solutions in optical devices, separations, catalysis, and beyond. Their tunability and eco-friendly synthesis further enhance their importance in chiral materials.
In this study, a new light-up fluorescent probe TCP was constructed based on flavonol framework. The probe TCP alone was almost non-emissive, while it exhibited a light blue fluorescence emission at 470 nm in the existence of Al3+. Meanwhile, this probe revealed a strong yellow fluorescence emission at 542 nm after the reaction with Hg2+. The probe TCP could selectively recognize and distinguish Al3+ and Hg2+ over other metal ions. This probe also possessed strong anti-interference ability and broad pH usage range during the detection of Al3+ and Hg2+. The detection limits of probe TCP for Al3+ and Hg2+ were computed to be as low as 0.196 mu M and 0.644 mu M. The probe TCP was competent for the quantitative assay of Hg2+ in actual environmental soil samples. Furthermore, the probe TCP was successfully employed for labeling the distributions of Al3+ and Hg2+ concentrations in living HepG2 cells.