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A sensitive and selective sensing system for chlorocatechols (3-chlorocatechol and 4-chlorocatechol) was developed based on Pseudomonas putida bacteria harboring the plasmid pSMM50R-B'. In this plasmid, the regulatory protein of the clc operon, ClcR, controls the expression of the reporter enzyme (beta)-galactosidase. When bacteria containing components of the clc operon are grown in the presence of chlorocatechols, ClcR activates the clcA promoter, which is located upstream from the (beta)-galactosidase gene. Thus, the concentration of chlorocatechols can be related to the production of (beta)-galactosidase in the bacteria. The concentration of (beta)-galactosidase expressed in the bacteria was determined by measuring the chemiluminescence signal emitted with the use of a 1,2-dioxetane substrate. ClcR has a high specificity for chlorocatechols and provides the sensing system with high selectivity. This was demonstrated by evaluating several structurally related organic compounds as potential interfering agents. Both 3-chlorocatechol and 4-chlorocatechol can be detected with this sensing system at concentrations as low as 8 x 10(super -10) and 2 x 10(super -9) M, respectively, using a 2-h induction period. In the case of 3-chlorocatechol, a highly selective sensing system was developed that can detect this species at concentrations as low as 6 x 10(super -8) M after a 5-min induction period; the presence of 4-chlorocatechol at concentrations as high as 2 x 10(super -4) M did not interfere with this system.

Development of new technologies with strong selectivity for target pollutants and low sensitivity toward a water matrix remains challenging. Herein, we introduced a novel strategy that used chlorite as an activator for Mn(VII) at pH 4.8, turning the inert reactivity of the pollutants toward Mn(VII) into a strong reactivity. This paved a new way for triggering reactions in water decontamination. By utilizing sulfamethoxazole (SMX) as a typical pollutant, we proposed coupled pathways involving electron transfer across hydrogen bonds (TEHB) and oxidation by reactive manganese species. The results indicated that a hydrogen bonding complex, SMX-ClO 2 - *, formed through chlorite binding the amino group of SMX initially in the TEHB route; such a complex exhibited a stronger reduction capability toward Mn(VII). Chlorite, in the hydrogen bonding complex SMX-ClO 2 - *, can then complex with Mn(VII). Consequently, a new reactive center (SMX-ClO 2 - -Mn(VII)*) was formed, initiating the transfer of electrons across hydrogen bonds and the preliminary degradation of SMX. This is followed by the involvement of the generated Mn(V)-ClO 2 - /Mn(III) in the reduction process of Mn(VII). Such a process showed pH-dependent degradation, with a removal ratio ranging from 80% to near-stagnation as pH increased from 4.8 to 7. Combining with p K a analysis showed that the predominant forms of contaminants were crucial for the removal efficiency of pollutants by the Mn(VII)/chlorite process. The impact of the water matrix was demonstrated to have few adverse or even beneficial effects. With satisfactory performance against numerous contaminants, this study introduced a novel Mn(VII) synergistic strategy, and a new reactivity pattern focused on reducing the reduction potential of the contaminant, as opposed to increasing the oxidation potential of oxidants.

Real-time monitoring of UAV motor speed is crucial for enhancing control performance and ensuring flight safety. However, this task faces challenges such as difficult sensor installation and high costs. This study introduces a wireless rotational speed sensing system based on a UAV-rotary triboelectric nanogenerator (UR-TENG). By employing a carefully designed structure with soft contact and a freestanding-triboelectric-layer mode, UR-TENG exhibits characteristics like low friction, affordability, ease of production, and self-powering capability. This eliminates the need for an external power source and addresses the complexity of installation in the limited space of UAVs. Experimental findings demonstrate that UR-TENG possesses high sensitivity and stability, maintaining the structural integrity of the UAV. The goodness of fit is notably high at 0.99959, with a maximum error rate of only 0.014 within a range of 6270 rpm. Moreover, UR-TENG integrates with a microcontroller unit (MCU) and external circuitry to form a monitoring system. This system transmits electrical signals to a PC via a Wi-Fi module, facilitating real-time rotational speed sensing and anomaly detection. Finally, a practical application demonstration on a UAV validates the adaptability of UR-TENG to complex operational environments. This study presents a promising approach for online rotation monitoring of UAV motors, with potential for commercialization, and introduces new avenues for TENG application in UAV technology.

Itaconic acid and its derivative 4-octyl itaconate (OI) represent a novel anti-inflammatory medication that has demonstrated efficacy in multiple inflammation models because of its minimal side effects. Recently, natural polymers conjugated with small molecule drugs, known as polymer-drug conjugates (PDCs), have emerged as a promising approach to sustained drug release. In this work, we reported an approach to prepare a PDC containing an OI and make it into an injectable hydrogel. Chitosan (CS) was selected for PDC synthesis because of its abundant free amino groups that can be conjugated with molecules containing carboxyl groups by carbodiimide chemistry. We used an ethanol/water cosolvent system to synthesize a CS-OI conjugate via EDC/NHS catalysis. The CS-OI conjugate had improved water solubility and unique anti-inflammatory activity and did not show compromised antibacterial activity compared with unmodified CS. Beta-glycerophosphate (β-GP) cross-linked CS-OI hydrogel exhibited good injectability with sustainable OI release and effectively modulated inflammatory response in a rat model. Therefore, this study provides valuable insights into the design of PDC hydrogels with inflammatory modulatory properties.

Biological-inorganic hybrid systems are a growing class of technologies that combine microorganisms with materials for a variety of purposes, including chemical synthesis, environmental remediation, and energy generation. These systems typically consider microorganisms as simple catalysts for the reaction of interest; however, other metabolic activity is likely to have a large influence on the system performance. The investigation of biological responses to the hybrid environment is thus critical to the future development and optimization. The present study investigates this phenomenon in a recently reported hybrid system that uses electrochemical water splitting to provide reducing equivalents to the nitrogen-fixing bacteria Xanthobacter autotrophicus for efficient reduction of N 2 to biomass that may be used as fertilizer. Using integrated proteomic and metabolomic methods, we find a pattern of differentiated metabolic regulation under electrochemical water-splitting (hybrid) conditions with an increase in carbon fixation products glycerate-3-phosphate and acetyl-CoA that suggests a high energy availability. We further report an increased expression of proteins of interest, namely, those responsible for nitrogen fixation and assimilation, which indicate increased rates of nitrogen fixation and support previous observations of faster biomass accumulation in the hybrid system compared to typical planktonic growth conditions. This work complicates the inert catalyst view of biological-inorganic hybrids while demonstrating the power of multiomics analysis as a tool for deeper understanding of those systems.

Laplace NMR is a powerful tool for studying molecular dynamics and spin interactions, providing diffusion and relaxation information that complements Fourier NMR used for composition determination and structure elucidation. However, Laplace NMR demands sophisticated signal processing algorithms such as inverse Laplace transform (ILT). Due to the inherently ill-posed nature of ILT problems, it is generally challenging to perform satisfactory Laplace NMR processing and reconstruction, particularly for two-dimensional Laplace NMR. Herein, we propose a proof-of-concept approach that blends a physics-informed strategy with data-driven deep learning for two-dimensional Laplace NMR reconstruction. This approach integrates prior knowledge of mathematical and physical laws governing multidimensional decay signals by constructing a forward process model to simulate relationships among different decay factors. Benefiting from a noniterative neural network algorithm that automatically acquires prior information from synthetic data during training, this approach avoids tedious parameter tuning and enhances user friendliness. Experimental results demonstrate the practical effectiveness of this approach. As an advanced and impactful technique, this approach brings a fresh perspective to multidimensional Laplace NMR inversion.

In the face of escalating global temperatures, the demand for innovative passive cooling technologies that are both low-cost and environmentally sustainable is more critical than ever. However, traditional cooling fabrics face challenges in achieving wearing comfort while maintaining breathability and durability. Herein, a novel fluffy microfibrous fabric utilizing polyolefin-elastomer and polypropylene with embedded zinc oxide nanoparticles is fabricated through melt-blown technology. The results reveal that the prepared samples demonstrate exceptional daytime radiative cooling properties that present a 12.5 °C cooling capacity under 1083 W/m 2 solar radiation, highlighted by their ability to reflect up to 90.8% of solar radiation and their significantly enhanced thermal emissivity. Moreover, key findings include that the samples have robust mechanical strength, high elastic performance, and excellent antifouling capabilities, alongside superior cooling performance, which will provide an opportunity to explore the development of cooling garments for outdoor environments and contribute substantially to sustainable cooling solutions.

Material-microbial interfaces offer a promising future in sustainable and efficient chemical-energy conversions, yet the impacts of these artificial interfaces on microbial metabolisms remain unclear. Here, we conducted detailed proteomic and metabolomic analyses to study the regulations of microbial metabolism induced by the photocatalytic material-microbial interfaces, especially the intracellular redox and energy homeostasis, which are vital for sustaining cell activity. First, we learned that the materials have a heavier weight in perturbing microbial metabolism and inducing distinctive biological pathways, like the expression of the metal-resisting system, than light stimulations. Furthermore, we observed that the materials-microbe interfaces can maintain the delicate redox balance and the energetic status of the microbial cells since the intracellular redox cofactors and energy currencies show stable levels as naturally inoculated microbes. These observations ensure the possibility of energizing microbial activities with artificial materials-microbe interfaces for diverse applications and also provide guides for future designs of materials-microbe hybrids to guard microbial activities.

Mixed components of formamidinium(FA) and cesium (Cs)-based perovskite solar cells are the most hopeful for commercialization owing to their excellent operational and phase stabilities, especially for devices with inverted structure. The nonradiative recombination of carriers can be effectively suppressed through interface optimization, therefore, the performance of devices can be improved. Notably, the buried interface emerges as critical aspects such as charge transport, charge recombination kinetics, and morphology of perovskite films. This study focuses on a straightforward yet effective approach to overcome buried interface challenges between organic polymers (poly(-triarylamine) (PTAA) and FACs-based perovskite films. The PTAA substrate is pretreated with a Lewis base known as 2-butynoic acid (BA) with a C═O functional group. First, it can be an interfacial buffering layer, harmonizing stress mismatch between the perovskite and PTAA layers, consequently optimizing crystallization and improving perovskite film quality. Second, Pb 2+ defect can be passivated at the buried interface of the perovskite film through binding with the C═O group of the BA molecule. This dual-function strategy leads to a substantial enhancement in both photoelectric conversion efficiency (PCE) and stability of devices. Finally, the PCE of the device-modified buried interface with BA reaches an impressive 23.33%. Furthermore, unencapsulated devices with BA treatment maintain approximately 94% of their initial efficiency after aging at maximum power point tracking for 1000 h.

Pickering double emulsions exhibit higher stability and biocompatibility compared with surfactant-stabilized double emulsions. However, tailored synthesis of particle stabilizers with appropriate wettability is time consuming and complicated and usually limits their large-scale adoption. Using binary stabilizers may be a simple and scalable strategy for Pickering double emulsion formation. Herein, commercially available hydrophobic silica nanoparticles (SNPs) and sodium alginate (SA) as binary stabilizers are used to prepare O/W/O Pickering double emulsions in one-step emulsification. The influence of system composition on double emulsion preparation is identified by optical microscopy, confocal laser scanning microscopy, and interfacial tension and water contact angle analyses. The formation of the O/W/O Pickering double emulsion depends critically on the aqueous phase viscosity and occurrence of emulsion inversion. Both hydrophobic SNPs and SA adsorb at the droplet surface to provide a steric barrier, while SA also reduces interfacial tension and increases aqueous phase viscosity, giving double emulsion long-term stability. Their microstructure and stability are controlled by adjusting the SA concentration, water-oil volume ratio, concentration and wettability of the particle stabilizer, and oil type. As a demonstration, the middle layer of the as-prepared O/W/O Pickering double emulsions can be cross-linked in situ with calcium ions to produce calcium alginate porous microspheres. We believe that our strategy for double emulsion formation holds great potential for practical applications in food, cosmetics, or pharmaceuticals.

Whole-grain foods are rich in bound polyphenols (BPs) whose health benefits were largely underestimated compared with free polyphenols. We first found that DFBP (dietary fiber with BPs from oat bran) exhibited stronger colonic antioxidant activities than DF. 16S rRNA sequencing showed that DFBP selectively changed gut microbial composition, which reciprocally released BPs from DFBP. Released polyphenols from DFBP reduced excessive colonic ROS and exhibited colonic antioxidant activities via the ROS/Akt/Nrf2 pathway revealed by transcriptome and western blot analysis. Colonic antioxidant activities of DFBP mediated by gut microbiota were next proven by treating mice with broad-spectrum antibiotics. Next, Clostridium butyricum , as a distinguished bacterium after DFBP intervention, improved colonic antioxidant capacities synergistically with DFBP in HFD-fed mice. This was explained by the upregulated mRNA expression of esterase, and cellulase of Clostridium butyricum participated in releasing BPs. Our results would provide a solid basis for explaining the health benefits of whole grains.

Determining the viability of a new drug molecule is a time- and resource-intensive task that makes computer-aided assessments a vital approach to rapid drug discovery. Here we develop a machine learning algorithm, iMiner, that generates novel inhibitor molecules for target proteins by combining deep reinforcement learning with real-time 3D molecular docking using AutoDock Vina, thereby simultaneously creating chemical novelty while constraining molecules for shape and molecular compatibility with target active sites. Moreover, through the use of various types of reward functions, we have introduced novelty in generative tasks for new molecules such as chemical similarity to a target ligand, molecules grown from known protein bound fragments, and creation of molecules that enforce interactions with target residues in the protein active site. The iMiner algorithm is embedded in a composite workflow that filters out Pan-assay interference compounds, Lipinski rule violations, uncommon structures in medicinal chemistry, and poor synthetic accessibility with options for cross-validation against other docking scoring functions and automation of a molecular dynamics simulation to measure pose stability. We also allow users to define a set of rules for the structures they would like to exclude during the training process and postfiltering steps. Because our approach relies only on the structure of the target protein, iMiner can be easily adapted for the future development of other inhibitors or small molecule therapeutics of any target protein.

Chronic kidney disease (CKD) has emerged as a significant public health concern. In this article, we investigated the mechanism of oat dietary fiber in regulating CKD. Our findings indicated that the gut microbiota of CKD patients promoted gut microbiota dysbiosis and kidney injury in CKD mice. Intervention with oat-resistant starch prepared by ultrasonic combined enzymatic hydrolysis (ORSU) and oat β-glucan with a molecular weight of 5 × 10 4 Da (OBGM) elevated the levels of short-chain fatty acids (SCFAs) and regulated gut dysbiosis in the gut-humanized CKD mice. ORSU and OBGM also reduced CKD-related uremic toxins such as creatinine, indoxyl sulfate (IS), and p -cresol sulfate (PCS) levels; reinforced the intestinal barrier function of the gut-humanized CKD mice; and mitigated renal inflammation and fibrosis via the NF-κB/TGF-β pathway. Therefore, ORSU and OBGM might delay the progression of CKD by modulating the gut microbiota to reduce uremic toxins levels. Our results explain the mechanism of oat dietary fiber aimed at mitigating CKD.

Poor hemostatic ability and less vascularization at the injury site could hinder wound healing as well as adversely affect the quality of life (QOL). An ideal wound dressing should exhibit certain characteristics: (a) good hemostatic ability, (b) rapid wound healing, and (c) skin appendage formation. This necessitates the advent of innovative dressings to facilitate skin regeneration. Therapeutic ions, such as silicon ions (Si 4+ ) and calcium ions (Ca 2+ ), have been shown to assist in wound repair. The Si 4+ released from silica (SiO 2 ) can upregulate the expression of proteins, including the vascular endothelial growth factor (VEGF) and alpha smooth muscle actin (α-SMA), which is conducive to vascularization; Ca 2+ released from tricalcium phosphate (TCP) can promote the coagulation alongside upregulating the expression of cell migration and cell differentiation related proteins, thereby facilitating the wound repair. The overarching objective of this study was to exploit short SiO 2 nanofibers along with the TCP to prepare TCPx@SSF aerogels and assess their wound healing ability. Short SiO 2 nanofibers were prepared by electrospinning and blended with varying proportions of TCP to afford TCPx@SSF aerogel scaffolds. The TCP x @SSF aerogels exhibited good cytocompatibility in a subcutaneous implantation model and manifested a rapid hemostatic effect (hemostatic time 75 s) in a liver trauma model in the rabbit. These aerogel scaffolds also promoted skin regeneration and exhibited rapid wound closure, epithelial tissue regeneration, and collagen deposition. Taken together, TCP x @SSF aerogels may be valuable for wound healing.

Humic acid (HA) is ubiquitous in natural aquatic environments and effectively accelerates decontamination by permanganate (Mn(VII)). However, the detailed mechanism remains uncertain. Herein, the intrinsic mechanisms of HA's impact on phenolics oxidation by Mn(VII) and its intermediate manganese oxo-anions were systematically studied. Results suggested that HA facilitated the transfer of a single electron from Mn(VII), resulting in the sequential formation of Mn(VI) and Mn(V). The formed Mn(V) was further reduced to Mn(III) through a double electron transfer process by HA. Mn(III) was responsible for the HA-boosted oxidation as the active species attacking pollutants, while Mn(VI) and Mn(V) tended to act as intermediate species due to their own instability. In addition, HA could serve as a stabilizer to form a complex with produced Mn(III) and retard the disproportionation of Mn(III). Notably, manganese oxo-anions did not mineralize HA but essentially changed its composition. According to the results of Fourier-transform ion cyclotron resonance mass spectrometry and the second derivative analysis of Fourier-transform infrared spectroscopy, we found that manganese oxo-anions triggered the decomposition of C-H bonds on HA and subsequently produced oxygen-containing functional groups (i.e., C-O). This study might shed new light on the HA/manganese oxo-anion process.

Colloidal activated carbon (CAC) is an emerging technology for the in situ remediation of groundwater impacted by per- and polyfluoroalkyl substances (PFAS). In assessing the long-term effectiveness of a CAC barrier, it is crucial to evaluate the potential of emplaced CAC particles to be remobilized and migrate away from the sorptive barrier. We examine the effect of two polymer stabilizers, carboxymethyl cellulose (CMC) and polydiallyldimethylammonium chloride (PolyDM), on CAC deposition and remobilization in saturated sand columns. CMC-modified CAC showed high mobility in a wide ionic strength (IS) range from 0.1 to 100 mM, which is favorable for CAC delivery at a sufficient scale. Interestingly, the mobility of PolyDM-modified CAC was high at low IS (0.1 mM) but greatly reduced at high IS (100 mM). Notably, significant remobilization (release) of deposited CMC-CAC particles occurred upon the introduction of solution with low IS following deposition at high IS. In contrast, PolyDM-CAC did not undergo any remobilization following deposition due to its favorable interactions with the quartz sand. We further elucidated the CAC deposition and remobilization behaviors by analyzing colloid-collector interactions through the application of Derjaguin-Landau-Verwey-Overbeek theory, and the inclusion of a discrete representation of charge heterogeneity on the quartz sand surface. The classical colloid filtration theory was also employed to estimate the travel distance of CAC in saturated columns. Our results underscore the roles of polymer coatings and solution chemistry in CAC transport, providing valuable guidelines for the design of in situ CAC remediation with maximized delivery efficiency and barrier longevity.

Ni-rich layered materials Li[Ni x Co y Mn z Al 1- x- y - z ]O 2 ( x > 0.8) are regarded as the competitive cathode for practical applications in lithium-ion batteries owing to the large discharging capacity. Nevertheless, the strong oxidation activity, the poor structure, and the thermal stability at the electrode-electrolyte interface would lead to much trouble, for example, inferior electrochemical properties and acute safety issues. To ameliorate the above problems, this work reports a strategy for the double modification of F - doping and LiNbO 3 covering in LiNi 0.88 Co 0.06 Mn 0.03 Al 0.03 O 2 cathode via using high-temperature calcining and ball-milling technology. As a result, the cathodes after F - doping and LiNbO 3 covering not only demonstrate a more stabilized crystal structure and particle interface but also reduce the release of high-activity oxygen species to ameliorate the thermal runaway. The electrochemical tests show that the LiNbO 3 -F - -modified cathode displays a superior rate capability of 159.3 mAh g -1 at 10.0 C and has the predominant capability retention of 92.1% in the 200th cycle at 25 °C, much superior than those (125.4 mAh g -1 and 84.0%) of bare cathode. Thus, the F- doped and LiNbO 3 -coated Ni-rich oxides could be a promising cathode to realize the high capacity and a stabilized interface.

Converting into high-value-added products represents the most optimal approach to CO 2 utilization. The substitution of CO with CO 2 as a potential critical material for formamide production is widely regarded as an ideal pathway and has garnered significant attention. However, high temperatures and pressures remain essential for the reaction, exerting a substantial influence on the utilization process. Herein, N -formylmorpholine was creatively synthesized by integrating the capture and solar-driven utilization of CO 2 with morpholine. Notably, a remarkable N -formylmorpholine yield of 11433.3 μmol·h -1 ·g -1 was obtained, surpassing pure MoO 3 by an astounding factor of 89.1 with a N -formylmorpholine yield of 63.8 μmol in 6 h, which is an astonishing increase of 57.5 times compared to MoO 3 . Both experimental results and density functional theory calculations suggest that the inclusion of Fe can effectively reduce the formation energy barrier while facilitating the desorption process of N -formylmorpholine, thereby optimizing the overall performance.

Mg(OH) 2 was used as the nanocarrier of the Bacillus thuringiensis (Bt) Cry1Ac protein, and the synthesized Cry1Ac-Mg(OH) 2 composites were regular and uniform nanosheets. Nano-Mg(OH) 2 could effectively improve the insecticidal effect of the Cry1Ac protein toward Ectropis obliqua . It could enhance the damage degree of the Cry1Ac protein to intestinal epithelial cells and microvilli, induce and enrich the production of reactive oxygen species (ROS) in the midgut, and enhance the degradation of the Cry1Ac protein into active fragments. Furthermore, an anti-rinsing assay showed that the Cry1Ac-Mg(OH) 2 composites were bound to the notch structure of the tea leaf surface. The retention of the Cry1Ac protein increased by 11.45%, and sprayed nano-Mg(OH) 2 was rapidly absorbed by different tissues of tea plants. Moreover, nano-Mg(OH) 2 and composites did not significantly affect non-target organisms. These results show that nano-Mg(OH) 2 can serve as a safe and effective biopesticide carrier, which provides a new approach for stable and efficient Bt preparation.

Restoration of blood-brain barrier (BBB) dysfunction, which drives worse outcomes of ischemic stroke, is a potential target for therapeutic opportunities, whereas a sealed BBB blocks the therapeutics entrance into the brain, making the BBB protection strategy paradoxical. Post ischemic stroke, hypoxia/hypoglycemia provokes the up-regulation of transmembrane glucose transporters and iron transporters due to multiple metabolic disorders, especially in brain endothelial cells. Herein, we develop a myricetin oligomer-derived nanostructure doped with Ce to bypass the BBB which is cointermediated by glucose transporters and iron transporters such as glucose transporters 1 (GLUT1), sodium/glucose cotransporters 1 (SGLT1), and transferrin(Tf) reporter (TfR). Moreover, it exhibits BBB restoration capacity by regulating the expression of tight junctions (TJs) through the activation of protective autophagy. The myricetin oligomers scaffold not only acts as targeting moiety but is the prominent active entity that inherits all diverse pharmacological activities of myricetin. The suppression of oxidative damage, M1 microglia activation, and inflammatory factors makes it a multitasking nanoagent with a single component as the scaffold, targeting domain and curative components.

Bacillus thuringiensis (Bt) is widely used to produce biological pesticides. However, its persistence is limited because of ultraviolet (UV) rays. In our previous study, we found that exogenous intermediates of the urea cycle were beneficial to Bt for survival under UV stress. To further explore the effect of the urea cycle on the resistance mechanism of Bt, the rocF / argG gene, encoding arginase and argininosuccinate synthase, respectively, were knocked out and recovered in this study. After the target genes were removed, respectively, the urea cycle in the tested Bt was inhibited to varying degrees. The UV stress test showed that the urea cycle disorder could reduce the resistance of Bt under UV stress. Meanwhile, the antioxidant enzyme activities of Bt were also decreased to varying degrees due to the knockout of the target genes. All of these results revealed that the urea cycle can metabolically regulate the stress resistance of Bt.

Diatomic-site catalysts (DASCs) inherit the excellent performance of single-atom catalysts (SACs) by utilizing two adjacent atomic metal species to achieve functional complementarity and synergistic effects that improve the carbon dioxide reduction reaction (CO 2 RR) and H 2 evolution reaction (HER) kinetics. Herein, we report a method to further improve the catalytic efficiency of Pt by using Pt and Ru single atoms randomly anchored on a g-C 3 N 4 surface, yielding partial Pt-Ru dimers. The synthesized catalyst exhibits extraordinary photocatalytic activity and stability in both the CO 2 RR and HER processes. In-depth experimentation, the pH-dependent chemical exchange saturation transfer (CEST) imaging nuclear magnetic resonance (NMR) method, and theoretical analyses reveal that the excellent performance is attributed to orbital coupling between the Pt atoms and the neighboring Ru atoms (mainly d xy and d xz ), which decreases the orbital energy levels and weakens the bond strength with intermediates, resulting in improved CO 2 RR and HER performance. This study successfully applies the pH-dependent CEST imaging NMR method to catalytic reactions, and CO 2 adsorption is directly observed using CEST 2D imaging maps. This work presents significant potential for a variety of catalytic reaction applications by systematically designing bimetallic dimers with higher activity and stability.

Current microflow cytometers suffer from complicated fluidic integration and low fluorescence collection efficiency, resulting in reduced portability and sensitivity. Herein, we demonstrated a new flow cell design based on an on-chip monolithically integrated microreflector with a bulk acoustic wave resonator (MBAW). It enables simultaneous 3D particle focusing and fluorescence enhancement without using shear flow. Benefited by the on-chip microreflector, the captured fluorescence intensity was 1.8-fold greater than that of the Si substrate and 8.3-fold greater than that of the SiO 2 substrate, greatly improving the detection sensitivity. Combined with the contactless acoustic streaming-based focusing, particle sensing with a coefficient of variation as low as 6.1% was achieved. We also demonstrated the difference between live and dead cells and performed a cell cycle assay using the as-developed microflow cytometry. This monolithic integrated MBAW provides a new type of opto-acoustofluidic system and has the potential to be a highly integrated, highly sensitive flow cytometer for applications such as in vitro diagnostics and point of care.

Copper-based compounds have attracted increasing attention as electrode materials for rechargeable devices, but their poor conductivity and insufficient stability inhibit their further development. Herein, an effective method has been proposed to improve the electrochemical properties of the copper-based electrodes by coating carbon materials and generating unique micro/nanostructures. The prepared Cu 2 S/Cu 7 S 4 /NC with hierarchical hollow structure possesses excellent electrochemical performance, attributing to the composition and structure optimization. The superior charge storage performance has been assessed by theoretical and experimental research. Specifically, the Cu 2 S/Cu 7 S 4 /NC exhibits remarkably higher electrical conductivity and lower adsorption-free energy for O* and OH* than those of Cu 2 O. Moreover, the Cu 2 S/Cu 7 S 4 /NC delivers a high specific capacitance of 1261.3 F·g -1 at the current density of 1 A·g -1 and also has great rate performance at higher current densities, which are much better than those of the Cu 2 O nanocubes. In addition, the assembled hybrid supercapacitor using Cu 2 S/Cu 7 S 4 /NC as the anode exhibits great energy density, power density, and cycling stability. This study has proposed a novel and feasible method for the synthesis of high-performance copper-based electrodes and their electrochemical performance regulation, which is of great significance for the advancement of high-quality electrode materials and rechargeable devices., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

Rh(III)-catalyzed C7-alkylation of isatogens (indolin-3-one N -oxides) with malonic acid diazoesters has been developed. This strategy utilizes oxygen anion on the N -oxide group of isatogens as a directing group and successfully achieves the synthesis of a series of C7-alkylated isatogens with moderate to good yields (48-86% yields). Moreover, the N -oxides of isatogens can not only serve as the simple directing group for C7-H bond cleavage but also be deoxidized for easy removal.

Excitonic effects significantly influence the selective generation of reactive oxygen species and photothermal conversion efficiency in photocatalytic reactions; however, the intrinsic factors governing excitonic effects remain elusive. Herein, a series of single-atom catalysts with well-defined M 1 -N 3 C 1 (M = Mn, Fe, Co, and Ni) active sites are designed and synthesized to investigate the structure-activity relationship between photocatalytic materials and excitonic effects. Comprehensive characterization and theoretical calculations unveil that excitonic effects are positively correlated with the number of valence electrons in single metal atoms. The single Mn atom with 5.93 valence electrons exhibits the weakest excitonic effects, which dominate superoxide radical (O 2 •- ) generation through charge transfer and enhance photothermal conversion efficiency. Conversely, the single Ni atom with 9.27 valence electrons exhibits the strongest excitonic effects, dominating singlet oxygen ( 1 O 2 ) generation via energy transfer while suppressing photothermal conversion efficiency. Based on the valence electron number dependent excitonic effects, a reaction environment with hyperthermia and abundant cytotoxic O 2 •- is designed, achieving efficient and stable water disinfection. This work reveals single metal atom dependent excitonic effects and presents an atomic-level methodology for catalytic application targeted reaction environment tailoring.

Bouquet is a fascinating wine characteristic that serves as an indicator of wine quality, developing during the aging process. The multifunctional monoterpenol oxidase VvCYP76F14 in wine grapes sequentially catalyzes three reactions to produce ( E )-8-carboxylinalool, a crucial precursor for wine bouquet. Previous studies indicated that the activity of VvCYP76F14 derived from different wine grape varieties did not correlate with the amino acid sequence differences. In this study, 54 wine grape varieties were categorized into neutral, aromatic, and full-bodied types based on the sequence differences of VvCYP76F14, closely correlated with the content of wine lactone precursors. Computer modeling and molecular docking analysis of the full-bodied CYP76F14 revealed 17, 19, and 18 amino acid residues in the VvCYP76F14-linalool, VvCYP76F14-( E )-8-hydroxylinalool, and VvCYP76F14-( E )-8-oxolinalool complexes, respectively. Site-directed mutagenesis and in vitro enzyme activity analysis confirmed the substitutions of the key amino acid residues in neutral and aromatic varieties. Notably, the D299 mutation of VvCYP76F14 resulted in the complete loss of ( E )-8-oxolinalool and ( E )-8-carboxylinalool activities, aligning with the undetectable levels of ( E )-8-oxolinalool and ( E )-8-carboxylinalool in "Yantai 2-3-37", which harbors the D299T substitution. Favorably, VvCYP76F14 could serve as a cost-effective fingerprint marker for screening superior hybrid offspring with the desired levels of wine lactone precursors.

The phenolic compounds (PCs) are the primary components responsible for the astringency of tea infusions, and this astringency is intricately linked to the in situ oral metabolism of PCs in saliva. Initially, a total of 54 PCs were identified in tea infusions by electrospray mass spectrometry (ESI-MS). Subsequently, an in vivo metabolism analysis of PCs during varying drinking times and oral locations was conducted by both paper spray mass spectrometry (PS-MS) and sensory evaluation. The metabolism of PCs within oral saliva was a prolonged process, the residual PCs were distributed across diverse oral regions after drinking tea infusion, and the higher residual PC content reflected the stronger astringency intensity. Furthermore, an in vitro metabolism analysis of PCs under varied reaction temperatures and durations was performed by ESI-MS and turbidimetry. As the reaction time extended, more PCs in tea was interacting with saliva. Moreover, the higher temperatures facilitated this interaction between PCs and saliva. Therefore, this investigation establishes a foundation for further elucidating the mechanisms underlying astringency formation.

Four typical dietary polyphenols ((-)-epigallocatechin gallate (EGCG), quinic acid (QA), caffeic acid (CA), and ferulic acid (FA)) were covalently prepared with rice recombinant human lactoferrin (OsrhLF) and bovine lactoferrin (bLF), and their structure and physicochemical properties were investigated, different lycopene emulsions were made by ultrasonic emulsification to analyze gastrointestinal fate. The results indicated that the covalent modification polyphenols changed the secondary/tertiary structure of LF, significantly improving the surface hydrophilicity, thermal stability, and antioxidant activity of LF. Compared with the bLF group, the OsrhLF group was more hydrophilic and the thermal denaturation temperature of the OsrhLF-CA reached 104.4 °C. LF-polyphenol emulsions significantly enhanced the photochemical stability and bioavailability of lycopene and achieved effective encapsulation and protection of lycopene compared to free lycopene, and the OsrhLF-EGCG reached 58.94% lycopene bioavailability. In short, OsrhLF does not differ much from bLF in terms of physicochemical properties and has a strong potential in the field of dietary supplements.

Over the past decades, significant progress has been made in utilizing nucleic acids, including DNA and RNA molecules, for therapeutic purposes. For DNA molecules, although various DNA delivery systems have been established, viral vector systems are the go-to choice for large-scale commercial applications. However, viral systems have certain disadvantages such as immune response, limited payload capacity, insertional mutagenesis and pre-existing immunity. In contrast, nonviral systems are less immunogenic, not size limited, safer, and easier for manufacturing compared with viral systems. What's more, nonviral DNA vectors have demonstrated their capacity to mediate specific protein expression in vivo for diverse therapeutic objectives containing a wide range of diseases such as cancer, rare diseases, neurodegenerative diseases, and infectious diseases, yielding promising therapeutic outcomes. However, exogenous plasmid DNA is prone to degrade and has poor immunogenicity in vivo . Thus, various strategies have been developed: (i) designing novel plasmids with special structures, (ii) optimizing plasmid sequences for higher expression, and (iii) developing more efficient nonviral DNA delivery systems. Based on these strategies, many interesting clinical results have been reported. This Review discusses the development of DNA-based nonviral gene therapy, including novel plasmids, nonviral delivery systems, clinical advances, and prospects. These developments hold great potential for enhancing the efficacy and safety of nonviral gene therapy and expanding its applications in the treatment of various diseases.

Metal coordination hydrogels (MC-HGs) that introduce dynamically coordinate bonds together with metal ionic conduction have attracted considerable attention in flexible electronics. However, the traditional soaking method alleged to have technical scalability faces the challenge of forming MC-HGs with a "core-shell" structure, which undoubtedly reduces the whole mechanical properties and ionic stimulation responsiveness required for flexible electronics materials. Herein, a novel strategy referred to as "masking" has been proposed based on the theory of the valence bond and coordination chemistry. By regulating the masking agents and their concentrations as well as pairing mode with the metal ions, the whole mechanical properties of the resulting composites (MC-HGs Masking ) show nearly double the values of their traditional soaking samples (MC-HGs Soaking ). For example, the fracture stress and toughness of Fe-HGs Masking (SA, 5.0 g/L) are 1.55 MPa and 2.14 MJ/m 3 , almost twice those of Fe-HGs Soaking (0.83 MPa and 0.93 MJ/m 3 , respectively). Microstructure characterization combined with finite element analysis, molecular dynamics, and first-principles simulations demonstrates that the masking strategy first facilitating interfacial permeation of metal complexes and then effective coordination with functional ligands (carboxylates) of the hydrogels is the mechanism to strengthen the mechanical properties of composites MC-HGs Masking , which has the potential to break through the limitations of current MC-HGs in flexible electronic sensor applications.

Noncontact human-machine interactions (HMIs) provide a hygienic and intelligent approach to communicate between humans and machines. However, current noncontact HMIs are generally hampered by the interaction distance, and they lack the adaptability to environmental interference such as high humidity conditions. Here, we explore a self-powered electret-based noncontact sensor (ENS) with moisture-resisting ability and ultrawide sensing range exceeding 2.5 m. A megascopic air-bubble structure is designed to enhance charge-storage stability and charge-recovery ability of the ENS based on the heterocharge-synergy effect in electrets. Besides, multilayer electret films are introduced to strengthen the electric field by utilizing the electrostatic field superposition effect. Thanks to the above improved performances of the ENS, we demonstrate various noncontact HMI applications in harsh environments, including noncontact appliances, a moving trajectory and accidental fall tracking system, and a real-time machine learning-assisted gesture recognition system with accuracy as high as 99.21%. This research expands the way for noncontact sensor design and may further broaden applications in noncontact HMIs.

Cytochrome P450 3A4 (CYP3A4), a prominent member of the P450 enzyme superfamily, plays a crucial role in metabolizing various xenobiotics, including over 50% of clinically significant drugs. Evaluating CYP3A4 inhibition before drug approval is essential to avoiding potentially harmful pharmacokinetic drug-drug interactions (DDIs) and adverse drug reactions (ADRs). Despite the development of several CYP inhibitor prediction models, the primary approach for screening CYP inhibitors still relies on experimental methods. This might stem from the limitations of existing models, which only provide deterministic classification outcomes instead of precise inhibition intensity (e.g., IC 50 ) and often suffer from inadequate prediction reliability. To address this challenge, we propose an uncertainty-guided regression model to accurately predict the IC 50 values of anti-CYP3A4 activities. First, a comprehensive data set of CYP3A4 inhibitors was compiled, consisting of 27,045 compounds with classification labels, including 4395 compounds with explicit IC 50 values. Second, by integrating the predictions of the classification model trained on a larger data set and introducing an evidential uncertainty method to rank prediction confidence, we obtained a high-precision and reliable regression model. Finally, we use the evidential uncertainty values as a trustworthy indicator to perform a virtual screening of an in-house compound set. The in vitro experiment results revealed that this new indicator significantly improved the hit ratio and reduced false positives among the top-ranked compounds. Specifically, among the top 20 compounds ranked with uncertainty, 15 compounds were identified as novel CYP3A4 inhibitors, and three of them exhibited activities less than 1 μM. In summary, our findings highlight the effectiveness of incorporating uncertainty in compound screening, providing a promising strategy for drug discovery and development.

Unveiling the effects of oxygen vacancies on the structural stability of layered α-MoO 3 is critical for optimizing its physical and chemical properties. Herein, we present experimental evidence regarding the phase stability of α-MoO 3 with ∼2% oxygen vacancy concentrations. Interestingly, we report a previously ignored oxygen-deficient orthorhombic MoO 3- x phase in space group Cmcm . Further density functional theory calculations reveal a detailed phase transition mechanism from α-MoO 3 to MoO 3- x . More importantly, we demonstrate that two-dimensional (2D) large polarons must exist to stabilize the MoO 3- x crystal structure. 2D large polarons are suspected to exist in numerous quasi-2D systems but have never been found in layered α-MoO 3 or other molybdenum oxides. Our work contributes to a basic understanding of the polaronic behavior in MoO 3- x and may broaden the application realm of molybdenum oxides.

In this study, we introduce the count-based Morgan fingerprint (C-MF) to represent chemical structures of contaminants and develop machine learning (ML)-based predictive models for their activities and properties. Compared with the binary Morgan fingerprint (B-MF), C-MF not only qualifies the presence or absence of an atom group but also quantifies its counts in a molecule. We employ six different ML algorithms (ridge regression, SVM, KNN, RF, XGBoost, and CatBoost) to develop models on 10 contaminant-related data sets based on C-MF and B-MF to compare them in terms of the model's predictive performance, interpretation, and applicability domain (AD). Our results show that C-MF outperforms B-MF in nine of 10 data sets in terms of model predictive performance. The advantage of C-MF over B-MF is dependent on the ML algorithm, and the performance enhancements are proportional to the difference in the chemical diversity of data sets calculated by B-MF and C-MF. Model interpretation results show that the C-MF-based model can elucidate the effect of atom group counts on the target and have a wider range of SHAP values. AD analysis shows that C-MF-based models have an AD similar to that of B-MF-based ones. Finally, we developed a "ContaminaNET" platform to deploy these C-MF-based models for free use.

Drug-induced liver injury (DILI) is a significant cause of drug failure and withdrawal due to liver damage. Accurate prediction of hepatotoxic compounds is crucial for safe drug development. Several DILI prediction models have been published, but they are built on different data sets, making it difficult to compare model performance. Moreover, most existing models are based on molecular fingerprints or descriptors, neglecting molecular geometric properties and lacking interpretability. To address these limitations, we developed GeoDILI, an interpretable graph neural network that uses a molecular geometric representation. First, we utilized a geometry-based pretrained molecular representation and optimized it on the DILI data set to improve predictive performance. Second, we leveraged gradient information to obtain high-precision atomic-level weights and deduce the dominant substructure. We benchmarked GeoDILI against recently published DILI prediction models, as well as popular GNN models and fingerprint-based machine learning models using the same data set, showing superior predictive performance of our proposed model. We applied the interpretable method in the DILI data set and derived seven precise and mechanistically elucidated structural alerts. Overall, GeoDILI provides a promising approach for accurate and interpretable DILI prediction with potential applications in drug discovery and safety assessment. The data and source code are available at GitHub repository (https://github.com/CSU-QJY/GeoDILI).

The introduction of thermostable polymerases revolutionized the polymerase chain reaction (PCR) and biotechnology. However, many GC-rich genes cannot be PCR-amplified with high efficiency in water, irrespective of temperature. Although polar organic cosolvents can enhance nucleic acid polymerization and amplification by destabilizing duplex DNA and secondary structures, nature has not selected for the evolution of solvent-tolerant polymerase enzymes. Here, we used ultrahigh-throughput droplet-based selection and deep sequencing along with computational free-energy and binding affinity calculations to evolve Taq polymerase to generate enzymes that are both stable and highly active in the presence of organic cosolvents, resulting in up to 10% solvent resistance and over 100-fold increase in stability at 97.5 °C in the presence of 1,4-butanediol, as well as tolerance to up to 10 times higher concentrations of the potent cosolvents sulfolane and 2-pyrrolidone. Using these polymerases, we successfully amplified a broad spectrum of GC-rich templates containing regions with over 90% GC content, including templates recalcitrant to amplification with existing polymerases, even in the presence of cosolvents. We also demonstrated dramatically reduced GC bias in the amplification of genes with widely varying GC content in quantitative polymerase chain reaction (qPCR). By expanding the scope of solvent systems compatible with nucleic acid polymerization, these organic solvent-resistant polymerases enable a dramatic reduction of sequence bias not achievable through thermal resistance alone, with significant implications for a wide range of applications including sequencing and synthetic biology in mixed aqueous-organic media.

SiZrOC aerogels were synthesized through the pyrolysis of the zirconium source-doped SiOC system using zirconyl chloride octahydrate (ZrOCl 2 ·8H 2 O) at temperatures ranging from 900 to 1300 °C. This study investigates the microstructure evolution and phase separation of SiOC and SiZrOC aerogels during the pyrolysis process. Upon pyrolysis, both aerogels exhibited a Si-O-C structure with a high thermal stability. The introduction of zirconium elements significantly enhanced the pore volume (3.20 cm 3 /g) and porosity (96.0%) and reduced the thermal conductivity (0.023 W·m -1 ·K -1 ) of the organic-inorganic precursor aerogel. Moreover, the three-dimensional pore structure was retained even under high-temperature pyrolysis conditions. SiZrOC-1100 displayed a high specific surface area of 273.52 m 2 /g, a high pore volume of 1.70 cm 3 /g, and a low thermal conductivity of 0.033 W·m -1 ·K -1 . At high temperatures, the SiZrOC phase transformation produces tetragonal ZrO 2 , which inhibits the graphitization process of free carbon and the growth of SiC grains. Furthermore, the phase separation process of the SiO x C y matrix structure generated oxygen-rich SiO x C 4- x units, while carbon-rich SiO x C 4- x units were negligible below a pyrolysis temperature of 1200 °C. Between 900 and 1200 °C, SiZrOC is composed of amorphous SiOC, amorphous ZrO 2 , microcrystalline t-ZrO 2 , and free carbon phase. These findings provide valuable insights into the preparation of high-performance SiOC aerogels.

Despite decades of research on phenols oxidation by permanganate, there are still considerable uncertainties regarding the mechanisms accounting for the unexpected parabolic pH-dependent oxidation rate. Herein, the pH effect on phenols oxidation was reinvestigated experimentally and theoretically by highlighting the previously unappreciated proton transfer. The results revealed that the oxidation of protonated phenols occurred via proton-coupled electron transfer (PCET) pathways, which can switch from ETPT (electron transfer followed by proton transfer) to CEPT (concerted electron-proton transfer) or PTET (proton transfer followed by electron transfer) with an increase in pH. A PCET-based model was thus established, and it could fit the kinetic data of phenols oxidation by permanganate well. In contrast with what was previously thought, both the simulating results and the density functional theory calculation indicated the rate of CEPT reaction of protonated phenols with OH - as the proton acceptor was much higher than that of deprotonated phenols, which could account for the pH-rate profiles for phenols oxidation. Analysis of the quantitative structure-activity relationships among the modeled rate constants, Hammett constants, and p K a values of phenols further supports the idea that the oxidation of protonated phenols is dominated by PCET. This study improves our understanding of permanganate oxidation and suggests a new pattern of reactivity that may be applicable to other systems.

As a key rate-limiting enzyme in the de novo synthesis of pyrimidine nucleotides, human dihydroorotate dehydrogenase ( h DHODH) is considered a known target for the treatment of autoimmune diseases, including inflammatory bowel disease (IBD). Herein, BAY 41-2272 with a 1 H -pyrazolo[3,4- b ]pyridine scaffold was identified as an h DHODH inhibitor by screening an active compound library containing 5091 molecules. Further optimization led to 2-(1-(2-chloro-6-fluorobenzyl)-1 H -pyrrolo[2,3- b ]pyridin-3-yl)-5-cyclopropylpyrimidin-4-amine ( w2) , which was found to be the most promising and drug-like compound with potent inhibitory activity against h DHODH (IC 50 = 173.4 nM). Compound w2 demonstrated acceptable pharmacokinetic characteristics and alleviated the severity of acute ulcerative colitis induced by dextran sulfate sodium in a dose-dependent manner. Notably, w2 exerted better therapeutic effects on ulcerative colitis than h DHODH inhibitor vidofludimus and Janus kinase (JAK) inhibitor tofacitinib. Taken together, w2 is a promising h DHODH inhibitor for the treatment of IBD and deserves to be developed as a preclinical candidate.

Recent research has primarily focused on the utilization of reductants as activators for Fe(VI) to generate high-valent iron species (Fe(IV)/Fe(V)) for the degradation of emerging organic contaminants (EOCs). However, a significant drawback of this approach arises from the reaction between reductants and ferrates, leading to a decrease in oxidation capacity. This study introduces a novel discovery that highlights the potential of the iron(III)-(1,10-phenanthroline) (Fe(III)-Phen) complex as an activator, effectively enhancing the degradation of EOCs by Fe(VI) and augmenting the overall oxidation capacity of Fe(VI). The degradation of EOCs in the Fe(VI)/Fe(III)-Phen system is facilitated through two mechanisms: a direct electron transfer (DET) process and electron shuttle action. The DET process involves the formation of a Phen-Fe(III)-Fe(VI)* complex, which exhibits a stronger oxidation ability than Fe(VI) alone and can accept electrons directly from EOCs. On the other hand, the electron shuttle process utilizes Fe(III)-Phen as a redox mediator to transfer electrons from EOCs to Fe(VI) through the Fe(IV)/Fe(III) or Fe(IV)/Fe(II)/Fe(III) cycle. Moreover, the Fe(III)-Phen complex can improve the utilization efficiency of Fe(V) by preventing its self-decay. This study's findings may present a viable option for utilizing an effective catalyst to enhance the oxidation of EOCs by Fe(VI) and Fe(V).

The emergence of green flexible aerogel electronics based on natural materials is expected to solve part of the global environmental and energy crisis. However, it is still challenging to achieve large-scale production and multifunctional stable applications of natural biomass fiber aerogel (BFA) materials. Herein, we exploit the interfacial bridging between the flower-type titanium dioxide nanoarray (FTNA) and natural fiber substrates to modulate the electronic structure and loss mechanism to achieve multifunctional properties. Specifically, the fibrous substrate with wrinkled features induces lattice strain in titania through precise interfacial bridging, effectively improving the intrinsic properties of the BFA materials. This interfacial bridging regulation strategy is also confirmed by X-ray absorption fine structure spectroscopy (XAS). More importantly, the construction of BFA products for different macroscopic and multifunctional applications through simple processing methods will facilitate the transition from natural materials to multifunctional flexible electronics. Therefore, the as-prepared blanket-type BFA (TCBFA) has good mechanical properties, electromagnetic protection properties, thermal stealth properties, high-temperature flame retardancy, and UV resistance. Meanwhile, the membrane-type (TCBFAM) multifunctional wearable fiber aerogel device exhibits superior flexibility, efficient Joule heating performance, and a smart response. This regulation strategy provides another concept for the design and innovation of green multifunctional fiber-integrated aerogels.

Polysaccharide-based QDs have attracted great attention in the field of biological imaging and diagnostics. How to get rid of the high heavy metal toxicity resulting from conventional Cd- and Pb-based QDs is now the main challenge. Herein, we offer a simple and environmentally friendly approach for the "direct" interaction of thiol-ending carboxymethyl chitosan (CMC-SH) with metal salt precursors, resulting in CuInS 2 QDs based on polysaccharides. A nucleation-growth mechanism based on the LaMer model can explain how CMC-CuInS 2 QDs are formed. As-prepared water-soluble CMC-CuInS 2 QDs exhibit monodisperse particles with sizes of 5.5-6.5 nm. CMC-CuInS 2 QDs emit the bright-green fluorescence at 530 nm when excited at 466 nm with the highest quantum yield of ∼18.0%. Meanwhile, the fluorescence intensity of CMC-CuInS 2 QD aqueous solution is quenched with the addition of Pb 2+ and the minimal limit of detection is as little as 0.4 nM. Furthermore, due to its noncytotoxicity, great biocompatibility, and strong biorecognition ability, CMC-CuInS 2 QDs can be exploited as a possible cell membrane imaging reagent. The imaging studies also demonstrate that CMC-CuInS 2 QDs are suitable for Pb 2+ detection in live cells and living organisms (zebrafish). Thus, this work offers such an efficient, green, and practical method for creating low-toxicity and water-soluble QD nanosensors for a sensitive and selective detection of toxic metal ion in live cells and organisms.

Ischemic stroke is a deleterious cerebrovascular disease with few therapeutic options, and its functional recovery is highly associated with the integrity of the blood-brain barrier and neuroinflammation. The Rho-associated coiled-coil containing protein kinase (ROCK) inhibitor fasudil (F) and the pyruvate dehydrogenase kinase (PDK) inhibitor dichloroacetate (DCA) have been demonstrated to exhibit neuroprotection in a series of neurological disorders. Hence, we synthesized and biologically examined the new salt fasudil dichloroacetate (FDCA) and validated that FDCA was eligible for attenuating ischemic volume and neurological deficits in the rat transient middle cerebral artery occlusion (tMCAO) model. Additionally, FDCA exerted superior effects than fasudil and dichloroacetate alone or in combination in reducing cerebral ischemic injury. Particularly, FDCA could maintain the blood-brain barrier (BBB) integrity by inhibiting matrix metalloproteinase 9 (MMP-9) protein expression and the degradation of zonula occludens (ZO-1) and Occludin protein. Meanwhile, FDCA could mitigate the neuroinflammation induced by microglia. The in vivo and in vitro experiments further demonstrated that FDCA disrupted the phosphorylations of myosin phosphatase target subunit 1 (MYPT1), mitogen-activated protein kinase (MAPK) cascade, including p38 and c-Jun N-terminal kinase (JNK), and pyruvate dehydrogenase (PDH) and limited excessive lactic acid metabolites, resulting in inhibition of BBB disruption and neuroinflammation. In addition, FDCA potently mitigated inflammatory response in human monocytes isolated from ischemic stroke patients, which provides the possibilities of a clinical translation perspective. Overall, these findings provided a therapeutic potential for FDCA as a candidate agent for ischemic stroke and other neurological diseases associated with BBB disruption and neuroinflammation.

The selective catalytic oxidation of NH 3 (NH 3 -SCO) to N 2 is an important reaction for the treatment of diesel engine exhaust. Co 3 O 4 has the highest activity among non-noble metals but suffers from N 2 O release. Such N 2 O emissions have recently been regulated due to having a 300× higher greenhouse gas effect than CO 2 . Here, we design CuO-supported Co 3 O 4 as a cascade catalyst for the selective oxidation of NH 3 to N 2 . The NH 3 -SCO reaction on CuO-Co 3 O 4 follows a de-N 2 O pathway. Co 3 O 4 activates gaseous oxygen to form N 2 O. The high redox property of the CuO-Co 3 O 4 interface promotes the breaking of the N-O bond in N 2 O to form N 2 . The addition of CuO-Co 3 O 4 to the Pt-Al 2 O 3 catalyst reduces the full NH 3 conversion temperature by 50 K and improves the N 2 selectivity by 20%. These findings provide a promising strategy for reducing N 2 O emissions and will contribute to the rational design and development of non-noble metal catalysts., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)