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Tetrahydropyridazines constitute an important structural motif found in numerous natural products and pharmaceutical compounds. Herein, we report an aminoacylation reaction of alkenes that enables the synthesis of 1,4,5,6-tetrahydropyridazines through cooperative N-heterocyclic carbene (NHC) and photoredox catalysis. This approach involves the 6-endo-trig cyclization of N-centered hydrazonyl radicals, generated via single-electron oxidation of hydrazones, followed by a radical-radical coupling step. The mild process tolerates a wide range of common functional groups and affords a variety of tetrahydropyridazines in moderate to high yields. Preliminary investigations using chiral NHC catalysts demonstrate the potential of this protocol for asymmetric radical reactions.
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The exploration of electrocatalysts toward oxygen reduction reaction (ORR) is pivotal in the development of diverse batteries and fuel cells that rely on ORR. Here, a FeCo-N-C electrocatalyst (FeCo-HNC) featuring with atomically dispersed dual metal sites (Fe-Co) and hollow cubic structure is reported, which exhibits high activity for electrocatalysis of ORR in alkaline electrolyte, as evidenced by a half-wave potential of 0.907 V, outperforming that of the commercial Pt/C catalyst. The practicality of such FeCo-HNC catalyst is demonstrated by integrating it as the cathode catalyst into an alkaline aluminum-air battery (AAB) paring with an aluminum plate serving as the anode. This AAB demonstrates an unprecedented power density of 804 mW cm-2 in ambient air and an impressive 1200 mW cm-2 in an oxygen-rich environment. These results not only establish a new benchmark but also set a groundbreaking record for the highest power density among all AABs reported to date. Moreover, they stand shoulder to shoulder with state-of-the-art H2-O2 fuel cells. This AAB exhibits robust stability with continuous operation for an impressive 200 h. This groundbreaking achievement underscores the immense potential and forward strides that the present work brings to the field.
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Flexible electronic devices, such as supercapacitors (SCs), place high demands on the mechanical properties, ionic conductivity, and electrochemical stability of electrolytes. Hydrogels, which combine flexibility and the advantages of both solid and liquid electrolytes, will meet the demand. Here, we report the synthesis of novel poly(ionic liquid)/polyacrylamide double-network (DN) (PIL/PAM DN) hydrogel electrolytes containing different metal salts via a two-step γ-radiation method. The resultant Li2SO4-1.0/PIL/PAM DN hydrogel electrolyte possesses excellent mechanical properties (tensile strength of 3.64 MPa, elongation at break of 446%) and high ionic conductivity (24.1 mS·cm-1). The corresponding flexible SC based on the Li2SO4-1.0/PIL/PAM DN hydrogel electrolyte (SC-Li2SO4) presents improved ion diffusion, ideal electrochemical double-layer capacitor behavior, good rate capability, and excellent cyclic stability. Moreover, symmetric SC-Li2SO4 achieves a wide operating voltage range of up to 1.5 V, with a maximum energy density of 26.0 W h·kg-1 and a capacitance retention of 94.1% after 10,000 galvanostatic charge-discharge cycles, owing to the deactivation of free water molecules by the synergistic effect of PIL, PAM, and SO42-. Above all, the capacitance of SC-Li2SO4 is well-maintained after overcharge, overdischarge, short circuit, extreme temperature, compression, and bending tests, indicating its high security and flexibility. This work reveals the enormous application potential of PIL-based conductive hydrogel electrolytes for flexible electronic devices.
RESUMEN
With the continuous operation of analog circuits, the component degradation problem gradually comes to the forefront, which may lead to problems, such as circuit performance degradation, system stability reductions, and signal quality degradation, which could be particularly evident in increasingly complex electronic systems. At the same time, due to factors, such as continuous signal transformation, the fluctuation of component parameters, and the nonlinear characteristics of components, traditional fault localization methods are still facing significant challenges when dealing with large-scale complex circuit faults. Based on this, this paper proposes a fault-diagnosis method for analog circuits using the ECWGEO algorithm, an enhanced version of the GEO algorithm, to de-optimize the 1D-CNN with an attention mechanism to handle time-frequency fusion inputs. Firstly, a typical circuit-quad op-amp dual second-order filter circuit is selected to construct a fault-simulation model, and Monte Carlo analysis is used to obtain a large number of samples as the dataset of this study. Secondly, the 1D-CNN network structure is improved for the characteristics of the analog circuits themselves, and the time-frequency domain fusion input is implemented before inputting it into the network, while the attention mechanism is introduced into the network. Thirdly, instead of relying on traditional experience for network structure determination, this paper adopts a parameter-optimization algorithm for network structure optimization and improves the GEO algorithm according to the problem characteristics, which enhances the diversity of populations in the late stage of its search and accelerates the convergence speed. Finally, experiments are designed to compare the results in different dimensions, and the final proposed structure achieved a 98.93% classification accuracy, which is better than other methods.
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The global sea surface temperatures (SSTs) are expected to change diversely in the future under different climate scenarios, which will affect the near-surface ozone (O3) distribution and concentration by influencing meteorological states and large-scale atmospheric circulation. Many countries have planned to reach carbon neutrality by the mid-21st century. In this study, the impacts of global and regional SST changes on near-surface O3 concentrations in China in the middle of the 21st century under the carbon-neutral scenario (Shared Socioeconomic Pathway 1-1.9), compared with the high-emission scenario (Shared Socioeconomic Pathway 5-8.5), and possible physical and chemical mechanisms are investigated using the Community Earth System Model version 1 (CESM1). Under future climate change, the changes in SSTs in the carbon-neutral scenario relative to the high-emission scenario lead to a dipole change in near-surface O3 concentrations in eastern and western China, with a significant decrease of 0.79 ppbv in the eastern China and a significant increase of 1.05 ppbv in the western China. The cooling of North Pacific Ocean under the carbon-neutral scenario causes a decrease in near-surface O3 concentrations by 0.48 ppbv in eastern China due to the weakened chemical production and an increase by 0.74 ppbv in western China attributed to the enhanced O3 transport from Eurasia. Cooling of Southern Hemisphere oceans leads to anomalous upward air motions over eastern China, which weaken the vertical transport of high-elevation O3 to the surface, resulting in a reduction in near-surface O3 concentrations by 0.58 ppbv in eastern China. Our results suggest that future changes in SSTs in the carbon-neutral scenario will positively benefit O3 air quality improvement in the polluted eastern China, with the North Pacific and Southern Hemisphere oceans playing important roles.
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Cancer immunotherapy is a promising method for cancer therapy. Imiquimod (R837) is a molecule that could activate immune systems for cancer immunotherapy, but an easily manufactured biocompatible carrier to deliver R837 may be needed to overcome the disadvantages of R837. Micelles formed by biocompatible copolymers have been widely used to deliver chemotherapeutic drugs but not immunotherapeutic drugs. In this study, R837 was linked to an amphiphilic biodegradable copolymer mPEG-b-PLA via acid-sensitive Schiff bases. The molecular structures were investigated by 1 H nuclear magnetic resonance, gel permeation chromatography and Fourier transform infrared spectroscopy. The product could be self-assembled into micelles with R837 content as high as 22.4%. Owing to acid-cleavable Schiff bases, the release of R837 from micelles was markedly accelerated under acidic media. Consequently, the micelles linked with R837 stimulated the expression of major histocompatibility complex II-stimulating molecules on the surface of RAW 264.7 macrophages at pH 6.5 but not pH 7.4. By using human umbilical vein endothelial cells as the in vitro model, it was shown that the polymer carriers and R837-linked micelles were minimally cytotoxic and did not induce the activation of endothelial cells under physiological pH, which suggested the relatively high biocompatibility. In conclusion, this study successfully developed pH-responsive immunotherapeutic drug-loaded micelles that could activate macrophages at acidic pH in vitro. The high biocompatibility of the micelles to endothelial cells also indicated the potential uses under in vivo conditions.