Anchoring and catalytic insights into bilayer C4N3 material for lithium-selenium batteries: a first-principles study.

In the present work, a theoretical design for the viability of bilayer C4N3 (bi-C4N3) as a promising host material for Li-Se battery was conducted utilizing first-principles calculations. The AA- and AB-stacking configurations of bilayer C4N3 can effectively inhibit the shuttling of high-order polyselenides through the synergistic effect of physical confinement and strong Li-N bonds. Compared to conventional electrolytes, the AA- and AB-stacking bilayer C4N3 demonstrate enhanced adsorption capabilities for the polyselenides. The anchored structures of Se8 or Li2Sen (n = 1, 2, 4, 6, 8) molecules within the bilayer C4N3 exhibit high electrical conductivities, which are beneficial for enhancing the electrochemical performance. The catalytic effects of AA- and AB-stacking bilayer C4N3 were investigated by the reduction of Se8 and the energy barrier associated with the decomposition of Li2Se. The AA- and AB-stacking bilayer C4N3 can significantly decrease the activation barrier and promote the decomposition of Li2Se. The mean square displacement (MSD) curves reveal the pronounceably sluggish Li-ions diffusions in polyselenides within the AA- and AB-stacking bilayer C4N3, which in turn demonstrates the notable prospects in mitigating the shuttle effect.

Multi-target direction-of-arrival estimation of deep models with frame-level permutation invariant training in marine acoustic environment.

Direction-of-arrival (DoA) estimation is an important part in sonar signal processing, providing a reliable foundation for tasks, such as underwater object detection and tracking. Although the deep learning model has powerful data fitting capabilities, accurately estimating the orientation of multiple targets with a single model remains a challenging task. To address this challenge, we enhance the permutation invariant training (PIT) technique and propose two different types of methods: multi-group classification with PIT (MC-PIT) and multi-group regression with PIT (MR-PIT). These two frame-level PIT schemes utilize a single model for both training and testing in multi-target scenarios. Furthermore, we evaluate the performance of MR-PIT and MC-PIT with different network backbones and demonstrate that the frame-level PIT has excellent portability. Compared with the model trained with the general multi-label strategy, simulation experiments show that our proposed methods have better multi-target DoA estimation performance. Finally, when the array configuration of simulated and recorded data are consistent, the model with frame-level PIT can achieve good performance on recorded data even only trained on simulation data.

Scalable Precise Nanofilm Coating and Gradient Al Doping Enable Stable Battery Cycling of LiCoO2 at 4.7†V.

The quest for smart electronics with higher energy densities has intensified the development of high-voltage LiCoO2 (LCO). Despite their potential, LCO materials operating at 4.7 V faces critical challenges, including interface degradation and structural collapse. Herein, we propose a collective surface architecture through precise nanofilm coating and doping that combines an ultra-thin LiAlO2 coating layer and gradient doping of Al. This architecture not only mitigates side reactions, but also improves the Li+ migration kinetics on the LCO surface. Meanwhile, gradient doping of Al inhibited the severe lattice distortion caused by the irreversible phase transition of O3-H1-3-O1, thereby enhanced the electrochemical stability of LCO during 4.7 V cycling. DFT calculations further revealed that our approach significantly boosts the electronic conductivity. As a result, the modified LCO exhibited an outstanding reversible capacity of 230 mAh g-1 at 4.7 V, which is approximately 28 % higher than the conventional capacity at 4.5 V. To demonstrate their practical application, our cathode structure shows improved stability in full pouch cell configuration under high operating voltage. LCO exhibited an excellent cycling stability, retaining 82.33 % after 1000 cycles at 4.5 V. This multifunctional surface modification strategy offers a viable pathway for the practical application of LCO materials, setting a new standard for the development of high-energy-density and long-lasting electrode materials.

Morphological and Coordination Modulations in Iridium Electrocatalyst for Robust and Stable Acidic OER Catalysis.

Proton exchange membrane water splitting (PEMWS) technology has high-level current density, high operating pressure, small electrolyzer-size, integrity, flexibility, and has good adaptability to the volatility of wind power and photovoltaics, but the development of both active and high stability of the anode electrocatalyst in acidic environment is still a huge challenge, which seriously hinders the promotion and application of PEMWS. In recent years, researchers have made tremendous attempts in the development of high-quality active anode electrocatalyst, and we summarize some of the research progress made by our group in the design and synthesis of PEMWS anode electrocatalysts with different nanostructures, and makes full use of electrocatalytic activity points to increase the inherent activity of Iridium (Ir) sites, and provides optimization strategies for the long-term non-decay of catalysts under high anode potential in acidic environments. At this stage, these research advances are expected to facilitate the research and technological progress of PEMWS, and providing some research ideas and references for future research on efficient and inexpensive PEMWS anode electrocatalysts.

Unveiling the anchoring and catalytic effect of Co@C3N3 monolayer as a high-performance selenium host material in lithium-selenium batteries: a first-principles study.

Suppressing the shuttle effect of high-order polyselenides is crucial for the development of high-performance host materials in lithium-selenium (Li-Se) batteries. Using first-principles calculations, the feasibility of Co@C3N3 monolayer as selenium cathode host material for Li-Se batteries is systematically evaluated from the aspects of binding energy, charge transfer mechanism, and catalytic effect of polyselenides in the present work. The Co@C3N3 monolayer can effectively prevent the solubilization of high-order polyselenides with large binding energy and charge transfer resulting from the synergistic effect of Li-N and Co-Se bonds. The polyselenides are inclined to adsorb on the surface of Co@C3N3 monolayer instead of interacting with the electrolytes, which effectively inhibits the shuttling of high-order polyselenides and improves cycling stability. The cobalt participation improves the conductivity of C3N3 monolayer, and the semi-metallic characteristics of the Co@C3N3 monolayer are maintained after the adsorption of Li2Sen (n = 1, 2, 4, 6, 8) or Se8 clusters, which is advantageous for the utilization of active selenium material. The crucial catalytic role of the Co@C3N3 monolayer is evaluated by examining the reduction pathway of Se8 and the decomposition barrier of Li2Se, and the results highlight the capability of Co@C3N3 monolayer to enhance the utilization of selenium and promote the transition of Li2Se. Our present work could not only provide valuable insights into the anchoring and catalytic effect of Co@C3N3 monolayer, but also shed light on the future investigation on the high performance C3N3-based host materials for Li-Se batteries.

Rh-Catalyzed Highly Enantioselective Hydrogenation of Functionalized Olefins with Chiral Ferrocenylphosphine-Spiro Phosphonamidite Ligands.

A highly efficient Rh-catalyzed hydrogenation of functionalized olefins has been realized by a new family of highly rigid chiral ferrocenylphosphine-spiro phosphonamidite ligands. Excellent enantiocontrol (>99% ee in most cases) was achieved with a wide range of α-dehydroamino acid esters and α-enamides. This practicable catalytic system was further applied in the scalable synthesis of highly optically pure key intermediates of cinacalcet and d-phenylalanine.

Effects of Silicon and Iron Application on Arsenic Absorption and Physiological Characteristics of Rice (Oryza sativa L.).

This study investigated the effects of silicon and iron on arsenic absorption, as well as the changes in the physiological indices of rice under arsenic stress and how these indices respond to silicon and iron. We found that application of silicon and iron reduces arsenic absorption in rice; co-application of silicon and iron reduced arsenic content by 25.6%-27.4%. The antioxidant enzyme activities of rice treated with silicon and iron were significantly lower than those of untreated rice, with the biggest decreases observed under co-application treatments. Iron significantly increased osmoregulatory substances, while silicon increased soluble sugar; Si1Fe1 treatment (containing 1 mM silicon, 0.1 mM iron) had the highest content of osmoregulatory substances except CK. Membership function analysis suggested that applying silicon and iron alone alleviates the stress condition in rice, with the lowest stresses observed under Si1Fe1 treatment. These results show that silicon and iron co-application significantly inhibits arsenic uptake in rice, decreases the antioxidant enzymes activity, while non-enzymatic substances in rice can be regulated to further alleviate arsenic stress.

Identification of key pathways and RNAs associated with skeletal muscle atrophy after spinal cord injury.

OBJECTIVE: This study was performed to investigate the potential key molecules involved in the progression of skeletal muscle atrophy after SCI. METHODS: Based on GSE21497 dataset, the DEmRNAs and DElncRNAs were screened after differentially expressed analysis. Then the enrichment analyses were performed on DEmRNAs. Then the PPI network and ceRNA network were constructed. Finally, the DGIdb was utilized to predict drug-gene interactions. RESULTS: A total of 412 DEmRNAs and 21 DElncRNAs were obtained. The DEmRNAs were significantly enriched in MAPK signaling pathway and FoxO signaling pathway. In addition, UBE2D1, JUN, and FBXO32 had higher node degrees in PPI network, and the top 20 genes with high degree were significantly enriched in FoxO signaling pathway and Endometrial cancer. Moreover, FOXO3 was regulated by hsa-miR-1207-5p and hsa-miR-1207-5p was regulated by lncRNA RP11-253E3.3 in ceRNA network. Finally, 37 drug-gene interactions were obtained based on the 26 genes in ceRNA network. CONCLUSION: UBE2D1, JUN, and FBXO32 are likely to be related to the progression of skeletal muscle atrophy after SCI, and activating of MAPK signaling pathway, Endometrial cancer and FoxO signaling pathway may induce skeletal muscle inflammation, apoptosis, autophagy and atrophy after SCI. Moreover, RP11-253E3.3-hsa-miR-1207-5p-FOXO3 axis may be a promising therapeutic target for skeletal muscle atrophy after SCI.

Robust and Stable Acidic Overall Water Splitting on Ir Single Atoms.

Single-atom electrocatalysts (SAEs) can realize the target of low-cost by maximum atomic efficiency. However, they usually suffer performance decay due to high energy states, especially in a harsh acidic water splitting environment. Here, we conceive and realize a double protecting strategy that ensures robust acidic water splitting on Ir SAEs by dispersing Ir atoms in/onto Fe nanoparticles and embedding IrFe nanoparticles into nitrogen-doped carbon nanotubes (Ir-SA@Fe@NCNT). When Ir-SA@Fe@NCNT acts as a bifunctional electrocatalyst at ultralow Ir loading of 1.14 µg cm-2, the required overpotentials to deliver 10 mA cm-2 are 250 and 26 mV for oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) in 0.5 M H2SO4 electrolyte corresponding to 1370- and 61-fold better mass activities than benchmark IrO2 and Pt/C at an overpotential of 270 mV, respectively, resulting in only 1.51 V to drive overall water splitting. Moreover, remarkable stability is also observed compared to Pt/C-IrO2.

Multi-exposure X-ray image fusion quality evaluation based on CSF and gradient amplitude similarity.

Due to the limitation of dynamic range of the imaging device, the fixed-voltage X-ray images often produce overexposed or underexposed regions. Some structure information of the composite steel component is lost. This problem can be solved by fusing the multi-exposure X-ray images taken by using different voltages in order to produce images with more detailed structures or information. Due to the lack of research on multi-exposure X-ray image fusion technology, there is no evaluation method specially for multi-exposure X-ray image fusion. For the multi-exposure X-ray fusion images obtained by different fusion algorithms may have problems such as the detail loss and structure disorder. To address these problems, this study proposes a new multi-exposure X-ray image fusion quality evaluation method based on contrast sensitivity function (CSF) and gradient amplitude similarity. First, with the idea of information fusion, multiple reference images are fused into a new reference image. Next, the gradient amplitude similarity between the new reference image and the test image is calculated. Then, the whole evaluation value can be obtained by weighting CSF. In the experiments of MEF Database, the SROCC of the proposed algorithm is about 0.8914, and the PLCC is about 0.9287, which shows that the proposed algorithm is more consistent with subjective perception in MEF Database. Thus, this study demonstrates a new objective evaluation method, which generates the results that are consistent with the subjective feelings of human eyes.

Recombinant PAL/PilE/FlaA DNA vaccine provides protective immunity against Legionella pneumophila in BALB/c mice.

BACKGROUND: Legionella pneumophila (L.pneumophila), a Gram-negative small microorganism, causes hospital-acquired pneumonia especially in immunocompromised patients. Vaccination may be an effective method for preventing L.pneumophila infection. Therefore, it is necessary to develop a better vaccine against this disease. In this study, we developed a recombinant peptidoglycan-associated lipoprotein (PAL)/type IV pilin (PilE)/lagellin (FlaA) DNA vaccine and evaluated its immunogenicity and efficacy to protect against L.pneumophila infection. RESULTS: According to the results, the expression of PAL, PilE, FlaA proteins and PAL/PilE/FlaA fusion protein in 293 cells was confirmed. Immunization with PAL/PilE/FlaA DNA vaccine resulted in highest IgG titer and strongest cytotoxic T-lymphocyte (CTL) response. Furthermore, the histopathological changes in lung tissues of mice challenged with a lethal dose of L.pneumophila were alleviated by PAL/PilE/FlaA DNA vaccine immunization. The production of T-helper-1 (Th1) cytokines (IFNγ, TGF-α, and IL-12), and Th2 cytokines (IL-4 and IL-10) were promoted in PAL/PilE/FlaA DNA vaccine group. Finally, immunization with PAL/PilE/FlaA vaccine raised the survival rate of mice to 100% after challenging with a lethal dose of L.pneumophila for 10 consecutive days. CONCLUSIONS: Our study suggests that the newly developed PAL/PilE/FlaA DNA vaccine stimulates strong humoral and cellular immune responses and may be a potential intervention on L.pneumophila infection.

PtRu nanoparticles embedded in nitrogen doped carbon with highly stable CO tolerance and durability.

As is well known, the lower durability and sluggish methanol oxidation reaction (MOR) of PtRu alloy electrocatalyst blocks the commercialization of direct methanol fuel cells (DMFCs). Here, we design a new PtRu electrocatalyst, with highly stable CO tolerance and durability, in which the PtRu nanoparticles are embedded in nitrogen doped carbon layers derived from carbonization of poly(vinyl pyrrolidone). The newly fabricated electrocatalyst exhibits no loss in electrochemical surface area (ECSA) and MOR activity after potential cycling from 0.6-1.0 V versus reversible hydrogen electrode, while commercial CB/PtRu retains only 50% of its initial ECSA. Meanwhile, due to the same protective layers, the Ru dissolution is decelerated, resulting in stable CO tolerance. Methanol oxidation reaction (MOR) testing indicates that the activity of newly fabricated electrocatalyst is two times higher than that of commercial CB/PtRu, and the fuel cell performance of the embedded PtRu electrocatalyst was comparable to that of commercial CB/PtRu. The embedded PtRu electrocatalyst is applicable in real DMFC operation. This study offers important and useful information for the design and fabrication of durable and CO tolerant electrocatalysts.

SiO2 decoration dramatically enhanced the stability of PtRu electrocatalysts with undetectable deterioration in fuel cell performance.

Prevention of Ru dissolution is essential for steady CO tolerance of anodic electrocatalysts in direct methanol fuel cells. Here, we demonstrate a facile way to stabilize Ru atoms by decorating commercial CB/PtRu with SiO2, which shows a six-fold higher stability and similar activity toward a methanol oxidation reaction leading to no discernible degradation in fuel cell performance compared to commercial CB/PtRu electrocatalysts. The higher stability and stable CO tolerance of SiO2-decorated electrocatalysts originate from the SiO2 coating, since Ru atoms are partially ionized during SiO2 decorating, resulting in difficulties in dissolution; while, in the case of commercial CB/PtRu, the dissolved Ru offers active sites for Pt coalescences and CO species resulting in the rapid decay of the electrochemical surface area and fuel cell performance. To the best of our knowledge, this is the first study about the stabilization of Ru atoms by SiO2. The highest stability is obtained for a PtRu electrocatalyst with negligible effect on the electrochemical properties.

Palladium Phosphide as a Stable and Efficient Electrocatalyst for Overall Water Splitting.

A palladium phosphide electrocatalyst supported on carbon black (PdP2 @CB) shows efficient water splitting in both alkaline and neutral electrolytes. Significantly lower overpotentials are required for PdP2 @CB (27.5 mV in 0.5 m H2 SO4 ; 35.4 mV in 1 m KOH; 84.6 mV in 1 m PBS) to achieve a HER electrocatalytic current density of 10 mA cm-2 compared to commercial Pt/CB (30.1 mV in 0.5 m H2 SO4 ; 46.6 mV in 1 m KOH; 122.7 mV in 1 m PBS). Moreover, no loss in HER activity is detectable after 5000 potential sweeps. Only 270 mV and 277 mV overpotentials are required to reach a current density of 10 mA cm-2 for PdP2 @CB to catalyze OER in 1 m KOH and 1 m PBS electrolytes, which is better OER activity than the benchmark IrO2 electrocatalyst (301 mV and 313 mV to drive a current density of 10 mA cm-2 ). 1.59 V and 1.72 V are needed for PdP2 @CB to achieve stable water splitting catalytic current density of 10 mA cm-2 in 1 m PBS and 50 mA cm-2 in 1 m KOH for 10 h, respectively.

Highly methanol-tolerant platinum electrocatalyst derived from poly(vinylpoyrrolidone) coating.

The design and fabrication of a methanol-tolerant electrocatalyst is still one of the most important issues in direct methanol fuel cells (DMFCs). Here, we focus on the design of a cathodic electrocatalyst in DMFCs and describe a new methanol-tolerant electrocatalyst fabricated from poly(vinylpyrrolidone) (PVP) coating on platinum nanoparticles assisted by hydrogen bonding between PVP and polybenzimidazole (PBI). The PVP layer has a negligible effect on the oxygen reduction reaction (ORR) activity, while the methanol oxidation reaction is retarded by the PVP layer. The PVP-coated electrocatalyst shows higher ORR activity under various methanol concentrations in the electrolyte, suggesting that the PVP-coated electrocatalyst has a higher methanol tolerance. Also, the PVP-coated electrocatalyst loses only 14% of the electrochemical surface area after 5000 potential cycles from 0.6-1.0 V versus the reversible hydrogen electrode, indicating better Pt stability than non-coated (27%) and commercial (38%) electrocatalysts due to the unique sandwich structure formed by the PVP and PBI. The power density of the PVP-coated electrocatalyst is four to five times higher compared to non-coated and commercial electrocatalysts with 12 M methanol feeding to the anode side, respectively. PVP coating is important for the enhancement of Pt stability and methanol tolerance. This study offers a new method for preparing a low-cost and high-methanol-tolerant Pt electrocatalyst, and useful information for real DMFC application to eliminate the methanol crossover problem in the cathode side.

Synthesis and Fluorescence Properties of Eu(3+), Tb(3+) Complexes with Schiff Base Derivatives.

Novel Schiff base ligands derived from N'-benzylidene-benzohydrazide (substituted by -H, -CH3, -OCH3, -Cl) and 2-chloro-N-phenylacetamide were synthesized. The solid complexes of rare earth (Eu, Tb) nitrate with these Schiff base ligands were synthesized and characterized by elemental analysis, EDTA titrimetric analysis, thermal analysis, infrared spectra and UV-Vis spectra analysis. The fluorescence properties of rare earth (Eu, Tb) complexes in solid were studied. Under the excitation of ultraviolet light, these complexes exhibited characteristic emission of europium and terbium ions. The results showed that the ligand favored energy transfer to the emitting energy of Eu and Tb ions. Effects of different ligands on the fluorescence intensity of rare earth (Eu, Tb) complexes had been discussed. The electrochemical properties of rare earth (Eu, Tb) complexes were also investigated.

Synthesis, characterization and properties of salicylhydrazide-salicylacylhydrazone derivatives and their terbium complexes.

A series of terbium complexes with salicylhydrazide-salicylacylhydrazone derivatives were synthesized and characterized by elemental analysis, IR spectra, UV/vis spectra and thermal analysis. The luminescence and electrochemical properties of the terbium complexes were investigated. The results show that all the target complexes exhibited characteristic emissions of terbium ions and the complex substituted by the chlorine has the strongest luminescence intensity with the highest quantum yield at 0.609. The introduction of donating electron groups could increase the oxidation potential and the highest occupied molecular orbital energy level of the terbium complex; however, the introduction of accepting electron groups gave the opposite result.

Synthesis, Characterization and Properties of Novel Coumarin Derivatives and Their Europium Complexes.

Seven novel coumarin derivatives derived from salicylaldehyde and phenol were synthesized and characterized by (1)H NMR and (13)C NMR spectra, mass spectra, infrared spectra and elemental analysis. Their corresponding Eu(III) complexes having general formula EuL(1-7)(NO3)3[Symbol: see text]2H2O were successfully prepared and characterized by elemental analysis, EDTA titrimetric, molar conductivity, UV-Vis, FT-IR and thermal performance studies. The luminescence properties, fluorescence quantum yields and the electrochemical properties of the title complexes were investigated. The results showed that the title complexes exhibited characteristic emissions of europium ions and possessed relatively good fluorescence quantum yields. The luminescence intensity of the complex with bromine-substituted group is the strongest among all the title complexes. The introduction of electron-withdrawing groups can increase the luminescence properties and fluorescence quantum yields, decrease the HOMO and LUMO energy levels of the title europium complexes, but electron-withdrawing group conversely. And these title complexes may possibly be useful for studying in luminescent materials field. Graphical Abstract Synthesis route of the ligands L (1-7).

Synthesis and properties of salicyladehyde salicyhydrazone derivatives and their europium complexes.

Four novel salicyladehyde salicyhydrazone derivatives and their corresponding europium (Eu(3+)) complexes were synthesized and characterized. The formulas of the complexes were [EuL(a-d)(NO3)2](NO3) · H2O. The investigatoin of fluoresence properties of the Eu(3+) complexes showed that the salicyladehyde salicyhydrazone derivatives were efficient sensitizers for the fluoresence of Eu(3+) ions. The fluorescence intensity of the complex substituted by methyl (-CH3) was the strongest among all the Eu(3+) complexes. The exploration of the electrochemical properties of the Eu(3+) complexes showed that the introduction of electron-donating groups methyl and methoxyl (-CH3 and -OCH3) could increase the oxidation potential and the highest occupied molecular orbital (HOMO) energy level of the Eu(3+) complex; however, the results of introduction of electron-withdrawing group were just opposite.

Gene expression profiles on predicting protein interaction network and exploring of new treatments for lung cancer.

In the present study, we aimed to explore disease-associated genes and their functions in lung cancer. We downloaded the gene expression profile GSE4115 from Gene Expression Omnibus (GEO) database. Total 97 lung cancer and 90 adjacent non-tumor lung tissue (normal) samples were applied to identify the differentially expressed genes (DEGs) by paired t test and variance analysis in spectral angle mapper (SAM) package in R. Gene Ontology (GO) functional enrichment analysis of DEGs were performed with Database for Annotation Visualization and Integrated Discovery, followed by construction of protein-protein interaction (PPI) network from Human Protein Reference Database (HPRD). Finally, network modules were analyzed by the MCODE algorithm to detect protein complexes in the PPI network. Total 3,102 genes were identified as DEGs at FDR < 0.05, including 1,146 down-regulated and 1,956 up-regulated DEGs. GO functional enrichment analysis revealed that up-regulated DEGs mainly participated in cell cycle and intracellular related functions, and down-regulated DEGs might influence cell functions. There were 39,240 pairs of PPIs in human obtained from HPRD databases, 3,102 DEGs were mapped to this PPI network, in which 2,429 pairs of PPIs and 1,342 genes were identified. With MCODE algorithm, 48 modules were selected, including five corresponding modules and three modules with differences in gene expressing profiles. In addition, three DGEs, FXR2, ARFGAP1 and ELAVL1 were discovered as potential lung cancer related genes. The discovery of featured genes which were probably related to lung cancer, has a great significance on studying mechanism, distinguishing normal and cancer tissues, and exploring new treatments for lung cancer.