A binder-free Ru@NiMoS electrode was engineered by in situ growth of two-dimensional NiMoS nanosheets on nickel foam. This process effectively promoted the electrostatic-driven aggregation of Ru(bpy)32+, harnessing the synergistic effect to enhance electrochemiluminescence (ECL) performance. The integration (Ru@NiMoS) achieved an impressive ECL efficiency of 70.1%, marking an impressive 36.9-fold enhancement over conventional Ru. Additionally, its ECL intensity was found to be remarkably 172.2 times greater than that of Ru. Within the Ru(bpy)32+/TPA system, NiMoS emerged as a pivotal electrochemical catalyst, markedly boosting both the oxygen evolution reaction and the generation of reactive intermediates. Leveraging these distinctive properties, a highly efficient ECL sensor for lidocaine detection was developed. This sensor exhibited a linear response within the concentration range of 1 nM to 1 μM and achieved a remarkably low detection limit of 0.22 nM, underlining its substantial potential for practical application.
Icing detection is critically important for preventing safety accidents and economic losses, especially concerning ice formation from invalidated anti-icing fluids (water and ethylene glycol) under extreme conditions. Traditional technologies like ultrasonics and capacitor-antenna face challenges with limited detection areas, lower accuracy, and susceptibility to electromagnetic interference. Here, we introduce a novel viscosity-ultrasensitive fluorescent probe 4′,4‴-(2,2-diphenylethene-1,1-diyl) bis-(3,5-dicarboxylate) (TPE-2B4C) based on AIEgens for monitoring ice formation of anti-icing fluids in low-temperature environments. TPE-2B4C, consisting of four sodium carboxylate groups and multiple freely rotating benzene rings, demonstrates outstanding solubility in anti-icing fluids and exhibits no fluorescent background signal even at low temperatures (<−20°C). Upon freezing, TPE-2B4C relocates from the water phase to higher viscosity ethylene glycol, causing restriction of benzene rings and a significantly increased green fluorescence signal. TPE-2B4C can successfully determine whether the anti-icing fluids are icing from −5 to −20°C with a high contrast ratio. Due to its simple setup, fast operation, and broad applicability, our new method is anticipated to be employed for rapid, real-time, and large-scale icing detection.
Surface-supported clusters forming by aggregation of excessive adatoms could be the main defects of 2D materials after chemical vapor deposition. They will significantly impact the electronic/magnetic properties. Moreover, surface supported atoms are also widely explored for high active and selecting catalysts. Severe deformation, even dipping into the surface, of these clusters can be expected because of the very active edge of clusters and strong interaction between supported clusters and surfaces. However, most models of these clusters are supposed to simply float on the top of the surface because ab initio simulations cannot afford the complex reconstructions. Here, we develop an accurate graph neural network machine learning potential (MLP) from ab initio data by active learning architecture through fine-tuning pre-trained models, and then employ the MLP into Monte Carlo to explore the structural evolutions of Mo and S clusters (1–8 atoms) on perfect and various defective MoS2 monolayers. Interestingly, Mo clusters can always sink and embed themselves into MoS2 layers. In contrast, S clusters float on perfect surfaces. On the defective surface, a few S atoms will fill the vacancy and rest S clusters float on the top. Such significant structural reconstructions should be carefully taken into account.
The soot emitted during the operation of diesel engine exhaust seriously threatens the human health and environment, so treating diesel engine exhaust is critical. At present, the most effective method for eliminating soot particles is post-treatment technology. Preparation of economically viable and highly active soot combustion catalysts is a pivotal element of post-treatment technology. In this study, different single-metal oxide catalysts with fibrous structures and alkali metal-modified hollow nanotubular Mn-based oxide catalysts were synthesized using centrifugal spinning method. Activity evaluation results showed that the manganese oxide catalyst has the best catalytic activity among the prepared single-metal oxide catalysts. Further research on alkali metal modification showed that doping alkali metals is beneficial for improving the oxidation state of manganese and generating a large number of reactive oxygen species. Combined with the structural effect brought by the hollow nanotube structure, the alkali metal-modified Mn-based oxide catalysts exhibit superior catalytic performance. Among them, the Cs-modified Mn-based oxide catalyst exhibits the best catalytic performance because of its rich active oxygen species, excellent NO oxidation ability, abundant Mn4+ ions (Mn4+/Mnn+ = 64.78%), and good redox ability. The T10, T50, T90, and CO2 selectivity of the Cs-modified Mn-based oxide catalyst were 267°C, 324°C, 360°C, and 97.8%, respectively.
We compared a range of BODIPY dimer derivatives without installing blocking groups by optimizing geometry structures and analyzing energies, frontier molecular orbitals, Chole&Cele map, electron density difference, spin-orbit coupling (SOC) matrix and decay rate constants from excited states. The dihedral angles of the β-β-linked BODIPY dimer and the α-α-linked BODIPY dimer tend to flatten in the T1 state, which is detrimental to the occurrence of the intersystem crossing (ISC). Conversely, the dihedral angle of the meso-β-linked BODIPY dimer, the meso-meso-linked BODIPY dimer and α-γ-linked BODIPY dimer is within the range of 125°–143° in the T1 state, facilitating ISC and the generation of singlet oxygen. Notably, the transition from S1 to S0 involving lowest unoccupied molecular orbital to highest occupied molecular orbital with long-wavelength emission and moderate oscillator strength underpins the remarkable long emission peaks observed experimentally for α-γ-linked BODIPY dimer. Moreover, the apparent SOC matrix enhances the ISC process, resulting in a respectable efficiency in generating singlet oxygen for this dimer. In meso-β-linked BODIPY, meso-meso-linked BODIPY, and α-γ-linked BODIPY, the S1→T1 process is characterized by a significant charge transfer, specifically transitioning from the 1CT state to the 3LE state, indicative of a spin-orbit charge transfer ISC (SOCT-ISC) mechanism. The ability to regulate the photosensitivity of BODIPY dimers by adjusting the dihedral angle between the two units in the T1 state unveils new avenues for designing high-performance photosensitizers for both therapeutic and imaging applications.
Desulfurization technology is rather difficult and urgently needed for carbon dioxide (CO2) utilization in industry. A new Cu(I)-based adsorbent was synthesized and examined for the capacity of removing carbonyl sulfide (COS) from a CO2 stream in an effort to solve the competitive adsorption between CO2 and COS and to seek opportunity to advance adsorption capacity. A wide range of characterization techniques were used to investigate the physicochemical properties of the synthesized Cu(I) adsorbent featuring π-complexation and their correlations with the adsorption performance. Meanwhile, the first principal calculation software CP2K was used to develop an understanding of the adsorption mechanism, which can offer useful guidance for the adsorbent regeneration. The synthesized Cu(I) adsorbent, prepared by using copper citrate and citric acid on the ZSM-5 (SiO2/Al2O3 = 25) carrier, outperformed other adsorbents with varying formulations and carriers in adsorption capacities. Through optimization of the preparation and adsorption conditions for various adsorbents, the breakthrough adsorption capacity (Qb) for COS was further enhanced from 2.19 mg/g to 15.36 mg/g. The formed stable π-complex bonds between COS and Cu(I), as confirmed by density functional theory calculations, were verified by the significant improvement in the adsorption capacity after regeneration at 600°C. The above advantages render the novel synthesized Cu(I) adsorbent a promising candidate featuring cost-effectiveness, high efficacy and good regenerability for desulfurization from a CO2 stream.
Organic luminophores with superior solid-state luminescence are urgently required in various fields, such as lighting, display, sensing, and solar energy conversion. However, to achieve their highly efficient luminescence still remains a challenge. Herein, a newly designed Nile red derivative, Nile-DPA-VB, is successfully obtained to exhibit aggregation-induced emission characteristics with the photoluminescent quantum yield (PLQY) of 11.45%. Such PLQY could be further promoted to 53.45% when Nile-DPA-VB is polymerized undergoing precipitation polymerization process, where the confined aggregation microenvironment severely restricts the intramolecular motions of Nile-DPA-VB. Remarkably, Nile-DPA-VB is ultrasensitive to the polarity and steric effect, enabling the real-time monitoring of aggregation microenvironment evolution for precipitation polymerization. The microphase separation and dynamic hardening for the nucleation and growth processes are visually demonstrated, which contribute dominantly to the high-efficiency luminescence. Finally, by doping the as-prepared fluorescent polymeric particles into polymethyl methacrylate, functional films with high luminescence and high haze are achieved to show the potential in lighting. These findings clearly demonstrate the significant role of polymerization in constructing high-efficiency solid-state luminescent materials for practice.
The COVID-19 pandemic has underscored the critical need for rapid and accurate diagnostic tools. Current methods, including Polymerase Chain Reaction and rapid antigen tests (RAT), have limitations in speed, sensitivity, and the requirement for specialized equipment and trained personnel. Nanotechnology, particularly upconversion nanoparticles (UCNPs), offer a promising alternative due to their unique optical properties. UCNPs can convert low-energy near-infrared light into higher-energy visible light, making them ideal for use as optical probes in single molecule detection and point of care applications. This study, initiated in early 2020, explores the opportunity of using highly doped UCNPs (40%Yb3+/4%Er3+) in lateral flow assay (LFA) for the early diagnosis of COVID-19. The UCNPs-based LFA testing demonstrated a minimum detection concentration of 100 pg/mL for SARS-CoV-2 antigen and 105 CCID50/mL for inactivated virus. Clinical trials, conducted in Malaysia and Western Australia independently, showed that the technique was at least 100 times more sensitive than commercial RAT kits, with a sensitivity of 100% and specificity of 91.94%. The development process involved multidisciplinary collaborations, resulting in the Virulizer device, an automated strip reader for point-of-care testing. This work sets a reference for future development of highly sensitive and quantitative RAT, aiming for the Limits of Detection in the range of sub-ng/mL.
Efficient recognition and selective capture of NH3 is not only beneficial for increasing the productivity of the synthetic NH3 industry but also for reducing air pollution. For this purpose, a group of deep eutectic solvents (DESs) consisting of glycolic acid (GA) and phenol (PhOH) with low viscosities and multiple active sites was rationally designed in this work. Experimental results show that the GA + PhOH DESs display extremely fast NH3 absorption rates (within 51 s for equilibrium) and high NH3 solubility. At 313.2 K, the NH3 absorption capacities of GA + PhOH (1:1) reach 6.75 mol/kg (at 10.7 kPa) and 14.72 mol/kg (at 201.0 kPa). The NH3 solubility of GA + PhOH DESs at low pressures were minimally changed after more than 100 days of air exposure. In addition, the NH3 solubility of GA + PhOH DESs remain highly stable in 10 consecutive absorption-desorption cycles. More importantly, NH3 can be selectively captured by GA + PhOH DESs from NH3/CO2/N2 and NH3/N2/H2 mixtures. 1H-NMR, Fourier transform infrared and theoretical calculations were performed to reveal the intrinsic mechanism for the efficient recognition of NH3 by GA + PhOH DESs.
The cell membrane, a fluid interface composed of self-assembled phospholipid molecules, is a vital component of biological systems that maintains cellular stability and prevents the invasion of foreign toxins. Due to its inherent fluidity, the cell membrane can undergo bending, shearing, and stretching, making membrane deformation crucial in processes like cell adhesion, migration, phagocytosis, and signal transduction. Within the plasma membrane are highly ordered dynamic structures formed by lipid molecules, known as “lipid rafts,” whose dynamic dissociation and reorganization are prerequisites for membrane deformation. Fluorescent probes have emerged as vital tools for studying these dynamic processes, offering a non-destructive, in situ, and real-time imaging method. By strategically designing these probes, researchers can image not only the microdomains of cell membranes but also explore more complex processes such as membrane fusion and fission. This review systematically summarizes the latest advancements in the application of fluorescent probes for cell membrane imaging. It also discusses the current challenges and provides insights into future research directions. We hope this review inspires further studies on the dynamic processes of complex cell membranes using fluorescent probes, ultimately advancing our understanding of the mechanisms underlying membrane dissociation, reorganization, fusion, and separation, and fostering research and therapeutic development for membrane-associated diseases.
Cellular senescence is a steady state of cell cycle arrest necessary to maintain homeostasis in organisms. However, senescent cells may cause senescence in neighboring healthy cells, inducing the onset of several diseases, such as inflammation, neurological disorders, and atherosclerosis. Therefore, early detection of cellular senescence is extremely important. β-Galactosidase (β-gal), as a critical marker of cellular senescence, can be monitored to facilitate early diagnosis of aging-related diseases. Furthermore, β-gal is mainly found in lysosomes, which have a pH value of about 4.5–5.5. Here, we developed a near-infrared fluorescent probe (QMOH-Gal) for tracking cell senescence in vitro and in vivo via the detection of β-gal. In addition, the probe displayed high sensitivity and specificity for β-gal with good fluorescence signal in the acidity range. Subsequently, this QMOH-Gal probe was successfully employed to differentiate between normal cells and senescent cells by monitoring β-gal. Furthermore, the probe not only realized the monitoring of β-gal in zebrafish but also the tracking of β-gal in palbociclib-induced breast tumor senescence. Overall, the probe shows great promise as an effective tool for imaging β-gal in vivo for studying the biology of aging in organisms.