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[Display omitted] • A novel type of PILs has been fabricated. • PILs integrate the permanent pores of porous solids with the exceptional properties of ILs. • PILs possess high activity and selectivity for the DBT oxidation. • IL moiety serves as an extractant to enrich DBT and creates an electrostatic solvent effect. • UiO-66 moiety serves as a catalysis to handily catalyze the ODS reaction. Developing a highly efficient strategy for the stabilization of the solid-liquid interface is a persistent pursuit for researchers. Herein, porous ionic liquids based on UiO-66 (Zr) porous materials were synthesized and applied to the selective desulfurization catalysis, which integrates the permanent pores of porous solids with the exceptional properties of ionic liquids. Results show that porous ionic liquids possess high activity and selectivity for dibenzothiophene. Experimental analysis and density functional theory calculations revealed that the ionic liquids moiety served as an extractant to enrich dibenzothiophene into the porous ionic liquids phase through the π···π and C H···π interactions. Additionally, the electrostatic solvent effect in the porous ionic liquids contributes to the stabilization solid-liquid interface, which was favorable for UiO-66 moiety to catalytically activate hydrogen peroxide (H 2 O 2) to generate ·OH radicals, and subsequently oxidized dibenzothiophene to the corresponding sulfone. It is hoped that the development of porous ionic liquids could pave a new route to the stabilization of the solid-liquid interface for catalytic oxidation. [ABSTRACT FROM AUTHOR]

Background: Mechanical damage to plants triggers local and systemic electrical signals that are eventually decoded into plant defense responses. These responses are constantly affected by other environmental stimuli in nature, for instance, light fluctuation. In recent years, studies on decoding plant electrical signals powered by various machine learning models are increasing in a sense of early prediction or detection of different environmental stresses that threaten plant growth or crop yields. However, the main bottleneck is the low-throughput nature of plant electrical signals, making it challenging to obtain a substantial amount of training data. Consequently, training these models with small datasets often leads to unsatisfactory performance. Results: In the present work, we set out to decode wound-induced electrical signals (also termed slow wave potentials, SWPs) from plants that are deprived of light to different extents. Using non-invasive electrophysiology, we separately collected sets of local and distal SWPs from the treated plants. Then, we proposed a workflow based on few-shot learning to automatically identify SWPs. This workflow incorporates data preprocessing, feature extraction, data augmentation and classifier training. We established the integral and the first-order derivative as features for efficiently classifying SWPs. We then proposed an Adversarial Autoencoder (AAE) structure to augment the SWP samples. Combining them, the Random Forest classifier allowed remarkable classification accuracies of 0.99 for both local and systemic SWPs. In addition, in comparison to two other reported methods, our proposed AAE structure enabled better classification results using our tested features and classifiers. Conclusions: The results of this study establish new features for efficiently classifying wound-induced electrical signals, which allow for distinguishing dark-affected local and systemic plant wound responses. We also propose a new data augmentation structure to generate virtual plant electrical signals. The methods proposed in this study could be further applied to build models for crop plants using electrical signals as inputs, and also to process other small-scale signals. [ABSTRACT FROM AUTHOR]

Biomass based active adsorbent can be prepared by activation process to adsorb dyes. In this study, using macroalgae as raw material, the biomass based activated carbon material was prepared by NaOH activation method to adsorb methylene blue. The activated adsorbent with high specific surface area (1238.491 m2 g−1) was characterized by BET, XRD, FTIR and XPS. The effects of impregnation ratio, amount of adsorbent, pH and contact time on the adsorption activity of biochar on MB were evaluated. The adsorption kinetics, molecular dynamics and density functional theory were discussed. The maximum MB removal efficiency of SWAC reached 98.56 % at 30 °C and pH = 5 which is due to its large specific surface area and mesoporous slit structure. MD simulation shows that MB molecules were adsorbed on carbon layer through face-to-face stacking. DFT calculation and subsequent electron structure analysis suggested that a synergistic effect of π-π stacking, cation-π interaction, and electrostatic interaction could help stabilize adsorbed MB molecules. And an excellent adsorption capacity SWAC is due to its graphitic N sites for high electronegativity. [ABSTRACT FROM AUTHOR]

Immune composition is commonly heterogeneous and varies among colorectal cancer (CRC) patients. A comprehensive immune classification may act as important characteristics to predict CRC prognosis. Thus, we aimed to identify novel immune specific subtypes to guide future therapies. Unsupervised clustering was used to classify CRC samples into different immune subtypes based on abundances of immune cell populations, during which TCGA and GSE17536 datasets were used as training and validation sets, respectively. The associations between the immune subtypes and patient prognosis were investigated. Further, we identified differentially expressed genes (DEGs) between immune high and low subtypes, followed by functional enrichment analyses of DEGs. The expression levels of 74 immunomodulators (IMs) across immune subtypes were analyzed. As a result, we clustered CRC samples into three distinct immune subtypes (immune high, moderate, and low). Patients with immune-high subtype showed the best prognosis, and patients with immune-low subtype had the worst survival in both TCGA and GSE17536 cohorts. A group of 2735 up-regulated DEGs were identified across immune high and low subtypes. The main DEGs were the members of complement components, chemokines, immunoglobulins, and immunosuppressive genes that are involved in immune modulation-related pathways (e.g., cytokine-cytokine receptor interaction) or GO terms (e.g., adaptive immune response and T cell activation). The expression levels of 63 IMs were significantly varied across immune subtypes. In conclusion, this study provides a conceptual framework and molecular characteristics of CRC immune subtypes, which may accurately predict prognosis and offer novel targets for personalized immunotherapy through modifying subtype-specific tumor immune microenvironment. [ABSTRACT FROM AUTHOR]

[Display omitted] • Fe single-atom adsorbents based on BNCO (Fe-BNCO) was synthesized. • Fe-BNCO-0.5 exhibits excellent adsortpin capacity for DBT (49.7 mg S/g). • Fe-doping results in a decrease of the crystallininty and a higher specific surface area. • The enhanced performance is sourced from the newly formed S-Fe coordination bond. Adsorbents with high adsorption capacity and selectivity have long been the pursuit of researchers in the field of adsorptive desulfurization. In this study, a novel single-atom adsorbent comprised of iron (Fe) integrated into C, O co-doped hexagonal boron nitride (Fe-BNCO) has been successfully synthesized. This unique material demonstrates outstanding adsorption capabilities, boasting an adsorption capacity of 49.7 mg S/g and excellent selectivity for adsorptive desulfurization. Notably, this adsorption capacity is 48.6 % higher than that of pure BNCO. The incorporation of the Fe element into boron nitride materials induces a reduction in crystallinity and an increase in specific surface area, resulting in a higher number of available adsorption sites. Combining experimental analysis with theoretical calculations, we propose that the exceptional adsorption performance of Fe-BNCO can be attributed to the formation of S-Fe coordination interaction, while maintaining the existing π-π interactions. This study advances our understanding of adsorbents with high adsorption capacity and selectivity, providing valuable insights for the field of adsorptive desulfurization. [ABSTRACT FROM AUTHOR]

Objectives. Sepsis is characterized as a dysregulated host immune response to infection and has been known to be closely associated with the gut microbiome. This study was aimed at investigating the gut microbial profiles of Zhuang ethnic patients with sepsis. Method. Eleven Zhuang ethnic patients with sepsis and 20 healthy individuals (controls) were recruited at the Baise City People's Hospital, China. Their gut microbial community profiles were analyzed by 16S rRNA gene sequencing using the Illumina MiSeq system. Results. The gut microbial community of patients with sepsis was significantly altered compared to that of the healthy individuals based on the results of principal coordinate analysis and microbial ecological networks. Additionally, significantly lower microbial alpha diversity was observed in patients with sepsis than in healthy individuals. In particular, the enrichment of Bilophila, Burkholderia, Corynebacterium, and Porphyromonas, along with the reduced abundance of a large number of short-chain fatty acid-producing microbes, including Roseburia, Bifidobacterium, Faecalibacterium, Coprococcus, Blautia, Clostridium, Ruminococcus, and Anaerostipe was observed in patients with sepsis compared to the control group. Moreover, patients with sepsis could be effectively classified based on the abundance of these bacteria using a support vector machine algorithm. Conclusion. This study demonstrated significant differences in the gut microbiome between Zhuang ethnic patients with sepsis and healthy individuals. In the future, it is necessary to determine whether such alterations are the cause or consequence of sepsis. [ABSTRACT FROM AUTHOR]

The Earth Exploration Satellite Service (EESS) for passive sensing has a primary frequency allocation in the 1400–1427 MHz band. All emissions unauthorized in this band are called RFI (Radio Frequency Interference). The SMOS (Soil Moisture and Ocean Salinity) mission is greatly perturbed by RFI impeding ocean salinity retrieval, especially in coastal areas such as the SCS (South China Sea), where the observed data has been discarded massively. At present, there is no way to eliminate the RFI impact on the retrieved salinity, other than by detecting and shutting down the emissions from the sources. However, it may be effective in a scientific sense if RFI can be quantified and applied to the salinity retrieval process. Therefore, this study proposes an RFI measuring method that can investigate contamination in both prominent and moderate respects, aroused either by on-site emissions or nearby continents. Based on the proposed method, two levels of hierarchical RFI maps of the SCS region, including the separated one and the merged one, are presented and discussed, indicating more severe contamination in northern and western SCS. Moreover, to verify the generalization of the method on open oceans far from continents, an area in the middle central Pacific is selected and tested. The result shows few or no RFI in this unattended region, which is consistent with the authors' knowledge. This study presents the concept of the "RFI map" to describe the contamination, which will hopefully help researchers comprehend the RFI state intuitively and assist in ocean salinity retrieval statistically. [ABSTRACT FROM AUTHOR]

The fabrication process of an advanced transparent cyclic olefin copolymer (COC)‐based laminate is introduced, along with the laser cutting technology for circuit pattern. Then, a three‐way Gysel divider with an equal power‐dividing ratio is reviewed, designed and measured, based on the proposed COC‐based laminate. The measured results are compared to those from a similar three‐way Gysel divider based on traditional RT/duroid 5880 laminate, from which we can see that COC‐based laminate has the advantage of lower loss, with other advantages such as low cost, easy realization, high‐precision, and even the transparency. This laminate can be an excellent candidate for a substrate at microwave or millimeter‐wave circuits. [ABSTRACT FROM AUTHOR]

[Display omitted] • The magnetic couplings of SrCaCoTeO 6 are significantly influenced by the A-site disorder. • The effect of A-site disorder can be negligible on the electronic structure. • All structures with different cationic arrangements show semiconducting nature. • The chemical combination is confirmed to be Sr2+Ca2+Co2+Te6+O2− 6. Herein, the effect of A-site disorder on the electronic structures and magnetic properties in double perovskite SrCaCoTeO 6 was systemically investigated using the first-principles calculations. Our results indicate that its magnetic coupling is significantly influenced by the A-site disorder, i.e., the ground magnetic properties vary with different cationic arrangement. However, this effect can be negligible on the electronic structure. Its semiconducting nature does not alter despite of different structures. Further analysis confirms that the B-site Co2+ is magnetic cation in the high-spin state with 3d7 (t 2g 5e g 2) electronic configuration, while Te at B′-site is nonmagnetic with no contribution to the magnetism. [ABSTRACT FROM AUTHOR]

Constructing reasonable pore structures and elements doping are significant for applying porous carbon materials in supercapacitors. Black humic acid is widely distributed in soils, waters and sediments, which inherently contains oxygen functional groups. In this research, black humic acid is used as a carbon source, and H 2 O 2 oxidation is synergistically applied with KOH activation to promote the formation of mesopores and enhance oxygen content to prepare the oxygen-rich and mesopore-rich hierarchical porous carbon material (HPC OA). HPC OA has a high oxygen content of 26.39 atom%, an abundant mesopore ratio of 87.00%, and a high specific surface area of 1727 m2·g-1. In a 6 M KOH electrolyte, the electrode material of HPC OA as a supercapacitor exhibits a specific capacitance of 226 F⋅g-1 at 0.2 A⋅g-1. The symmetric electrodes exhibit an energy density of 11.28 Wh⋅kg−1 with a power density of 60.00 W⋅kg−1 and the capacitor retention are 98.53% after 6000 cycles. The research proposes a new strategy from hierarchical porous carbon materials to regulate the mesoporous formation and oxygen doping, providing carbon electrode materials for supercapacitors with excellent performance. [Display omitted] [ABSTRACT FROM AUTHOR]

Background: Reverse Transcription quantitative polymerase chain reaction (RT-qPCR) is a sensitive and reliable method for mRNA quantification and rapid analysis of gene expression from a large number of starting templates. It is based on the statistical significance of the beginning of exponential phase in real-time PCR kinetics, reflecting quantitative cycle of the initial target quantity and the efficiency of the PCR reaction (the fold increase of product per cycle). Results: We used the large clinical biomarker dataset and 94-replicates-4-dilutions set which was published previously as research tools, then proposed a new qPCR curve analysis method——CqMAN, to determine the position of quantitative cycle as well as the efficiency of the PCR reaction and applied in the calculations. To verify algorithm performance, 20 genes from biomarker and partial data with concentration gradients from 94-replicates-4-dilutions set of MYCN gene were used to compare our method with various publicly available methods and established a suitable evaluation index system. Conclusions: The results show that CqMAN method is comparable to other methods and can be a feasible method which applied to our self-developed qPCR data processing and analysis software, providing a simple tool for qPCR analysis. [ABSTRACT FROM AUTHOR]

• Dynamic loaded tooth contact analysis (DLTCA) for computing entrainment speed. • Accurate solution to elastohydrodynamic lubrication (EHL) governing equation. • Discrete convolution and fast Fourier transformation (DC-FFT) for flank elastic deformation. • A separation flow method for iteration of EHL governing equation. • Accurate entrainment effect-based EHL forecasting model for hypoid gears. In full consideration of time-varying meshing performance and oil film characteristics, entrainment effect on elastohydrodynamic lubrication (EHL) is developed for establishing accurate forecasting model of the complex hypoid gears. Firstly, dynamic loaded tooth contact analysis (DLTCA) is employed to determine the meshing interface kinematics, load distribution and entrainment speed under dynamic load condition. Then, entrainment speed is introduced into the EHL governing equation and accurate forecasting model is established. With accurate discretization of EHL governing equation, discrete convolution and fast Fourier transformation (DC-FFT) method is employed to compute the flank elastic deformation. Finally, a hypoid gear set in automotive industrial application is exercised to verify entrainment effect on EHL assessment in the proposed model. [ABSTRACT FROM AUTHOR]

• Expression of miR-149 in sperm is correlated with the quality of early embryonic development. • Sperm-borne miR-149 is not required for early embryonic development but serve as an adjunct biomarker. • miR-149 could be used as a first indication of early embryonic development. miRNAs play a critical role in the regulation of highly orchestrated gene expression profiles during spermatogenesis and early human embryonic development. However, there is much less information available on the effects of sperm-borne miRNAs on human embryonic development than on spermatogenesis. This study was designed to assess the relationship between two sperm-borne miRNAs (miR-34c and miR-149) and preimplantation embryo development in conventional in vitro fertilization treatment. A positive correlation was seen between a decreased level of miR-149 and a higher percentage of good-quality embryos on day 3 in conventional in vitro fertilization treatment (P < 0.0001), but no correlation was seen between miR-34c and a higher percentage of good-quality embryos (P = 0.1084). Receiver-operating characteristic curve analysis and logistic regression analysis showed that sperm-borne miR-149 with decreased expression was significantly associated with a high rate of good-quality embryos (area under the curve 0.781) (odds ratio: 0.078, 95 % confidence interval: 0.024−0.259, P < 0.0001). Our results demonstrate that the expression profile of miR-149 with significantly decreased expression could be used as a first indication of early embryonic development and may provide novel insight into the biological background of idiopathic infertile males. [ABSTRACT FROM AUTHOR]

Carbon materials prepared by biomass pyrolysis have been studied for conversion of lignin into phenols. In this study, the control mechanism of free radicals on phenolic products selectivity was studied using guaiacol as a model chemical. The results showed that gaseous radicals or carbon-centered radicals of carbon materials could promote phenols formation through different mechanisms. In gas-phase system, the selectivity of phenols was mainly controlled by methyl radicals which led to a theoretical selectivity of phenols lower than 50%. In the heterogeneous system, methyl radicals and phenolic radicals were easily and rapidly adsorbed on the carbon edge sites. The o-hydroxyphenoxy radical was the key intermediate and was firstly absorbed on the carbon center radical sites where phenols produced at the same position after undergoing desorption and hydrogenation. In conclusion, the present study concluded that conversion of lignin to phenols can proceed rapidly as long as there are carbon-centered radicals distributed at zigzag edge on the carbon surface. • A comprehensive gaseous pyrolysis reaction mechanism of guaiacol was revealed. • DFT was used to determine the carbon sites that act as active site in the lignin biochar co pyrolysis process. • Gas-phase free radicals and carbon defect control mechanisms of demethoxy reaction were systematically compared. [ABSTRACT FROM AUTHOR]

This study proposes a compact structure of the three‐way Gysel power divider with arbitrary power dividing ratio, which has a significant difference from existing N‐way ones with a common node in the centre of the circuit. First, existing equations are reviewed, and new analytical closed‐form equations are derived according to the proposed structure. The frequency bandwidths, affected by the parameters of isolation networks are investigated in detail and optimised for performance balance. For verification, the proposed three‐way Gysel power dividers are calculated, optimised and fabricated at the centre frequency of 3.5GHz with different dividing ratios of 1:1:1 and 1:2:3, respectively. Moreover, the equations are derived to design the N‐way Gysel power divider. [ABSTRACT FROM AUTHOR]

• PFOA exposure induces apoptosis in human ovarian granulosa cells. • GJIC may be the primary target for PFOA-induced ovarian granulosa cell apoptosis. • PFOA exposure has potential adverse effects on female reproductive health. Perfluorooctanoic acid (PFOA) has attracted widespread research attention as it is very stable, bioaccumulates, and causes reproductive toxicity. Data from several animal experiments and epidemiological studies indicate that female fertility may decline because of ovarian granulosa cell (GC) apoptosis as oocyte quality is positively associated with effective gap junctional intercellular communication (GJIC) between GCs. To the best of our knowledge, however, no previous trials have been conducted or reported on the effects of PFOA exposure on apoptosis induction in human GCs. Moreover, the roles of GJIC in GC survival and in the induction of apoptosis in GCs by PFOA remain unclear. To test this, we cultured human GCs in vitro and treated them with 0 μM, 0.3 μM, 3 μM, or 30 μM PFOA for 24 h. We also treated a human ovarian GC line (KGN) with various combinations of PFOA, retinoic acid (RA, 10 μM), and carbenoxolone disodium (CBX, 50 mM). Our findings showed that PFOA lowered human GC viability and increased apoptosis. The effects of CBX resemble those of PFOA. The combination of PFOA and CBX enhances the inhibition of GJIC by PFOA and promotes apoptosis. The effects of RA are the opposite to those of PFOA. The combination of RA and PFOA mitigates PFOA-induced GJIC inhibition and reduces apoptosis. The observed expression levels of apoptosis-related proteins were consistent with the aforementioned findings. Hence, our study demonstrated that PFOA may induce human ovarian GC apoptosis by inhibiting GJIC. [ABSTRACT FROM AUTHOR]

Half-metals have drawn extensive interest due to their unique electronic structure and wide application in spintronics. We report an A-site-ordered quadruple perovskite CeCu3Cr4O12 with half-metallic behaviors using first-principles calculations. Our calculations demonstrate that CeCu3Cr4O12 is a ferrimagnet with a saturated magnetic moment of 7.00 μB f.u.–1. Effective ferrimagnetic interactions are generated from the antiparallel spin arrangement between the A′-site Cu and B-site Cr. The electronic structure analyses reveal that CeCu3Cr4O12 exhibits half-metal performance, which can be attributed to the mixed-valence of B-site Cr. More importantly, a small amount of 4f itinerant electrons are located on the A-site Ce, i.e., both itinerant electron magnetism and localized magnetic moments are observed in the theoretical calculations. The charge distribution in this system is confirmed to be Ce(4−δ)+Cu2+3Cr(3.5+δ)+4O2−12. The physical properties of the AA′3B4O12-type perovskite CeCu3Cr4O12 revealed in this study show that this class of materials shows promise in applications of half-metals. [ABSTRACT FROM AUTHOR]

• NGS was used for characterizing miRNA profiles in seminal plasma with different SDF. • Differential miRNAs expression in seminal plasma with different SDF. • Decreased expression of miR-374b and miR-26b as a first indication of increased SDF. • miR-374b and miR-26b as adjunct biomarkers for diagnosing idiopathic infertile males. Sperm DNA fragmentation index (SDF), as an important supplement to routine semen parameters, has been proposed to discriminate between fertile and infertile men, and predicts the outcomes of natural conception and in vitro fertilization. Unfortunately there are uncertainty and contradictory evidences regarding the importance of SDF. An important reason is the fact that significant and fundamental research about SDF is rare. This study was designed to characterize the microRNA (miRNA) expression profile in seminal plasma of normospermic patients with different SDF and their implications in human fertility. Using next-generation sequencing (NGS), a total of 897 human miRNAs were detected from 10 seminal plasma samples, out of which 431 differentially expressed miRNAs in 5 pairs of seminal plasma samples (each pair of seminal plasma samples obtained from the same male), with 14 miRNAs were identified in all the pairs. According to the fold change and expression level, 7 miRNAs including miR-374b-5p, miR-429, hsa-miR-26b-5p, miR-21−5p, miR-4257, miR-135b-5p and miR-134−5p were selected for further excavation. MiR-374b-5p and miR-26b-5p were significantly different in 3 sets of individual seminal plasma samples with different SDF from total 90 infertile patients (30 patients each set). Our results demonstrate that the profile of miR-374b and miR-26b with significantly decreased expression could be used as a first indication of increased SDF. And miR-374b and miR-26b could serve as adjunct biomarkers for the diagnosis of idiopathic infertile males. [ABSTRACT FROM AUTHOR]

The direct bandgap nature of semiconductors is crucial for a wide range of optoelectronic devices and energy applications. These materials are mainly concentrated in hybrid organic–inorganic halide perovskites, III–V semiconductors, and monolayer transition metal dichalcogenides. Here, we report an AA′3B2B′2O12-type direct bandgap semiconductor CaCu3Fe2Ta2O12 using spin-polarized density functional theory calculations. The formation energy indicates that this material is thermodynamically preferred under a high-temperature and high-pressure synthetic route, similar to the analog CaCu3Fe2Nb2O12. Effective ferrimagnetic interaction occurs through the antiferromagnetic coupling between the A-site Cu and B-site Fe. More importantly, CaCu3Fe2Ta2O12 exhibits semiconducting behavior with a direct bandgap in the visible range, suggesting that AA′3B2B′2O12-type quadruple perovskites are potential candidate materials in photovoltaics as well as in optoelectronic devices. [ABSTRACT FROM AUTHOR]

In this work, salix mongolica, pretreated by FeCl3 and ZnCl2, was applied as a precursor to prepare the magnetic biochar (MBC, containing γ-Fe2O3) with the method of one-step pyrolysis. According to the characterization results of MBC (SEM, XPS, XRD, FTIR, VSM, BET), the features of biochar and the magnetic properties of iron oxides were combined in a composite of MBC. The magnetic biochar can be used as adsorbent for sulfadimidine sodium (SMS) and norfloxacin (NOR) removal from aqueous solution and subsequently removed from the medium by a simple magnetic process. The adsorption characteristics of SMS and NOR from aqueous solution by MBC have been investigated. The adsorption kinetics was best described by Elovich model. The equilibrium data was best fitted by the Freundlich isotherm and Koble-Corrigan model implying the adsorption process mainly was multilayer adsorption on heterogeneous surfaces. The maximum adsorption capacity for SMS and NOR was 251 mg/g and 210 mg/g at 308 K, respectively. The values of thermodynamic parameters were calculated indicating the process of adsorption was an endothermic and spontaneous process. The adsorption mechanism may be attributed to the π–π dispersion, the hydrophobic interaction, hydrogen bonding or the electrostatic interaction between the MBC and the molecule of NOR or SMS. [ABSTRACT FROM AUTHOR]

Metal/oxide heterointerfaces are ubiquitous in functional materials, and their microstructures frequently govern the macroscopic properties. It has been believed that the interfacial interactions are very weak at incoherent interfaces with large mismatches. Combining atomic-resolution scanning transmission electron microscopy with density functional theory calculations, we investigated the interaction and bonding reconstruction at Pd/ZnO{0001} interfaces, which have large mismatches. Molecular beam epitaxy was employed to grow Pd films on clean Zn-terminated ZnO(0001) and O-terminated ZnO(000 1 ¯) polarized surfaces. Atomically sharp Zn-terminated interfaces formed on both substrates, and the large lattice misfits between them were not strongly accommodated, suggesting the formation of incoherent regions. The interfacial atoms were located almost at bulk lattice points in the stoichiometric Zn-terminated Pd(111)/ZnO(0001) structure, whereas the interfacial Pd and Zn atoms underwent relatively large relaxations on the interfacial plane in the nonstoichiometric Zn-terminated Pd(111)/ZnO(000 1 ¯ ) interface. Effective Pd–Zn chemical bonds were formed across both interfaces, but the bonding mechanisms were quite different, depending on the local atomic geometry. The Pd–Zn bonds exhibited site-dependent characteristics and gradually transitioned from covalent to ionic at the Pd(111)/ZnO(0001) interface, whereas most of Pd–Zn bonds exhibited strong covalent behavior at the Pd/ZnO(000 1 ¯ ) interface. The adhesive energies indicated that the Zn-terminated Pd/ZnO(000 1 ¯ ) interface is energetically preferable to the Zn-terminated Pd/ZnO(0001) interface. Thus, the interfacial interaction can be strong and direct metal–metal interactions can play a critical role in metal/oxide heterointerfaces with large mismatches, opening up a new avenue for understanding the origins of interface-related issues. Image 1 [ABSTRACT FROM AUTHOR]

Temperature induced intermetallic charge transfer and negative thermal expansion in compounds hold promise for many applications. Here, we report, by the first-principles calculations, the mechanism behind these effects and the associated electrical and magnetic properties of an A-site-ordered perovskite LaCu3Fe4O12. We find that the sensitive expansion of Cu-O bonds to temperature can trigger a transformation from Cu3+ to Cu2+, which imposes a covalent state transition of B-site Fe from +3 to +3.75. The resultant shrinkage of the Fe-O bonds is demonstrated to play a pivotal role in the volume contraction of the oxide at high temperatures. [ABSTRACT FROM AUTHOR]

The magnetic and electronic structures of LaMn3Cr4O12 are investigated using the full-potential linearized augmented plane wave method within both the generalized gradient approximation (GGA) and GGA + U (electronic correlation) methods. The calculated results indicate that LaMn3Cr4O12 is an antiferromagnetic insulator. The magnetic ordering is demonstrated to be G-type within both Mn-site and Cr-site spins. However, there is no obvious magnetic coupling between Mn-site and Cr-site sublattices, which is verified by the separate distribution of their corresponding partial density of states. Moreover, the magnetic coupling constants of JCr-Cr and JMn-Mn are predicted to be - 5.0 (- 2.8) and - 0.83 (- 0.63) meV within GGA (GGA + U), respectively, consistent with the experimentally observed two independent Néel temperatures (TN1 and TN2). The calculated densities of states reveal the experimentally reported charge formula of LaMn3+3Cr3+4O12. [ABSTRACT FROM AUTHOR]

The charge degree of freedom of A-site cation as well as B-site cation plays a significant role in determining the internal charge distribution and gives rise to fascinating physical properties in perovskite oxides. Here, we discuss the magnetic couplings and electronic structures of rare-earth Ce cation incorporated A-site-ordered quadruple perovskite CeMn 3 Mn 4 O 12 via first-principles calculations. This report demonstrates that the A site Ce is magnetic cation with quantity of 4 f electrons, which is quite different from the nonmagnetic Ce4+ usually found in isostructural compounds. As a result, not only the A′ and B site manganese sublattices but also the A site cerium sublattice is involved in the complex magnetic interactions. In the low-temperature phase, CeMn 3 Mn 4 O 12 is ferrimagnetic with the Ce(↓)-Mn1(↑)-Mn2(↓)-Mn3(↑)-Mn4(↑)-Mn5(↓) type, in which the effective magnetic couplings are generated from A-site Ce sublattice as well as the antiparallel arrangement within both the A and B site manganese sublattices. The analysis of electronic structure reveals the valence distribution is Ce3+Mn3+ 3 Mn3+ 4 O2- 12 where both the oxidation state of Ce and Mn is +3. Nevertheless, ferromagnet is the most favorable in energy with a large saturated magnetic moment at the high-temperature phase. Interestingly, the electronic structure undergoes a semiconducting to half-metallic transition accompanying with the phase transformation. The present results offer a new strategy to realizing the tunable charge distribution via variable valence A site cation in A-site-ordered quadruple perovskites and thus open an avenue to modulate these materials with exotic properties. [Display omitted] • CeMn 3 Mn 4 O 12 is ferrimagnetic with the Ce(↓)-Mn1(↑)-Mn2(↓)-Mn3(↑)-Mn4(↑)-Mn5(↓) type in the low-temperature phase. • Ferromagnet is the most favorable in energy with a large saturated magnetic moment at the high-temperature phase. • The A-site Ce sublattice is magnetic with a small quantity of 4f electrons within both phases. • A semiconducting to half-metal transition is realized accompanying with the temperature-induced phase transformation. [ABSTRACT FROM AUTHOR]

Lithium–sulfur (Li‐S) batteries have become one of the most promising candidates as next‐generation batteries, owing to their high specific capacity, low cost, and environmental benignity. Although many strategies have been proposed to restrain the shuttle of lithium polysulfides (LiPSs) through physical trapping and chemical binding, the sluggish kinetics of PS conversion still degrade the capacity, rate, and cycling performance of Li‐S batteries. Herein, a novel kind of few‐layer BN with engineered nitrogen vacancies (v‐BN) has been developed as a cathode matrix for Li‐S batteries. The positive vacancies in the BN nanosheets not only promote the immobilization and conversion of LiPSs, but also accelerate the lithium ion diffusion in cathode electrodes. Compared with pristine BN, the v‐BN cathodes exhibit higher initial capacities from 775 mA h g−1 to 1262 mA h g−1 at 0.1 C and a high average coulombic efficiency of over 98 % during 150 cycles. Upon increasing the current density to 1 C, the cell still preserves a capacity of 406 mA h g−1 after 500 cycles, exhibiting a capacity decay of only 0.084 % per cycle. The new vacancy‐engineered material provides a promising method for achieving excellent performance in Li‐S batteries. [ABSTRACT FROM AUTHOR]

Highlights • Sn based DESs with urea were firstly synthesized and introduced into hexagonal boron nitride. • Sn based DESs with urea were served as both reaction solvents and metal sources. • These materials present higher adsorption capacity for dibenzothiophene (DBT) from model oils. • The nature of the ADS source from the π-complexation and hydrogen bonding interaction between SnO 2 and DBT. Graphical abstract Sn based DESs with urea were firstly synthesized and introduced into hexagonal boron nitride. These materials present higher adsorption capacity for dibenzothiophene (DBT) from model oils. The nature of the ADS source from the π-complexation and hydrogen bonding interaction between SnO 2 and DBT. Abstract Adsorptive desulfurization (ADS) from fuels is considered as the most promising strategy due to the advantage of low energy consumption, to treat on sulfur which would induce serious air pollution. In this work, Sn-based DESs with urea were firstly synthesized and introduced into hexagonal boron nitride (h-BN) as both reaction solvents and metal sources. Adsorption experiments show that the as-prepared adsorbents present higher adsorption capacity for dibenzothiophene (DBT) from model oils as compared with the commercial BN. Especially, the Sn-BN-800 (SnO 2 supported BN with OH groups substitution at B sites) shows the highest performance. By combining experimental and theoretical analysis, we propose that the performance enhancement arises from the π-complexation and hydrogen bonding interaction between SnO 2 and DBT. In addition, the OH groups, which were substituted at the edge site of B, may also enhance the electron transfer from DBT to Sn-BN-800, leading to the improved adsorption capacity. [ABSTRACT FROM AUTHOR]

Graphical abstract The interlayer-expanded 1 T-MoSe 2 cocatalyst modified 2D-C 3 N 4 exhibits an ultra-high hydrogen evolution rate of 1672.6 μmol g−1 h−1 with AQE of 5.2% at 420 nm. The giant improved HER performance can be ascribed to the enhanced charge separation efficiency and favorable hydrogen evolution capacity of cocatalyst. Highlights • The interlayer-expanded 1T-MoSe 2 is for the first time utilized as cocatalyst in photocatalytic hydrogen evolution. • The MoSe 2 cocatalyst can effectively boost the HER performance of 2D-C 3 N 4 with AQE = 5.2% at 420 nm. • The interlayer-expanded 1T-phase structure leads to favorable hydrogen evolution capacity of MoSe 2 benifiting for HER. Abstract Visible-light-driven photocatalytic hydrogen evolution reaction (HER) is of far-reaching significance to address the energy and environmental issues. Owing to the seriously limited charge separation and surface catalytic conversion efficiency, cocatalyts especially noble-metals (e.g. Pt) are fundamentally required for this reaction. Transitional metal dichalcogenides (TMDs) represent a type of promising nonprecious cocatalysts, but they still lack effective strategies to optimize the performance. In this work, we report a rational design of MoSe 2 to form interlayer-expanded 1T-phase structure, to maximize the cocatalytic activity for photocatalytic HER by optimizing the surface activation ability for reaction molecule at both edge and basal sites. In a practical photocatalytic reaction, when intergrated with a semiconductor (two-dimensional carbon nitride, 2D-C 3 N 4), the hybrid exhibits a satisfactory hydrogen evolution rate (1672.6 μmol g−1 h−1, with external quantum efficiency of 5.2% at 420 nm) that greatly higher than the normal spacing 2H-MoSe 2 (186.7 μmol g−1 h−1) and most noble-metals (e.g. Au, Ag, Pd). The giant improved HER performance strongly demonstrates the superiority of the presented phase and interlayer engineering strategy. The formation mechanism of the specialized structure and the key factor affecting the performance are also discussed. This work may provide new avenues for the design of TMDs-based catalysts toward HER application. [ABSTRACT FROM AUTHOR]

A series of the Eu 3+ -activated Gd 2 W 1- x Mo x O 6 phosphors were synthesized by a high-temperature solid-state reaction method. The phase composition, ultraviolet-visible diffuse reflectance spectra, photoluminescence and decay properties of the phosphors were investigated. Through adjusting the Mo 6+ ion concentration, the excitation band of the studied sample was gradually shifted to longer wavelength. Under 376 nm excitation, the strong red emission at 610 nm and weak yellow emission centered at 591 nm were detected, indicating that Eu 3+ occupies non-inversion symmetry sites in the host lattices. With elevating the dopant concentration, the emission intensity of synthesized products was greatly enhanced and achieved its optimum value when x  = 0.95 which was 2.33 times higher than that of the Gd 2 WO 6 :Eu 3+ compounds. The quantum efficiency of resultant samples was as high as 76.1%. Moreover, the Judd-Oflet theory was used to study the local structure environment behaviors of the Eu 3+ ions in the host lattices. Finally, a red LED device, which consisted of a near-ultraviolet chip and prepared Gd 2 W 0.05 Mo 0.95 O 6 :Eu 3+ phosphors, was successfully fabricated. These results confirmed that the Eu 3+ -doped Gd 2 W 1- x Mo x O 6 phosphors have potential value as the red component for WLEDs. [ABSTRACT FROM AUTHOR]

Hydrogen peroxide (H 2 O 2 ) decomposition mechanism and its oxidative desulfurization activity on hexagonal boron nitride monolayer (h-BN) have been explored by density functional theory (DFT) at M06–2X/6-311 + G (d,p) level. A cluster model which contains seven rings has been constructed to simulate the h-BN surface. It is found that 7 possible species will be generated after the decomposition of H 2 O 2 . Among them, 2H*+O 2 * and 2H*+2O* are relatively unstable while other species, such as HOO*+H*, HO*+HO*, H*+HO + O*, H 2 O*+O* are relatively stable and may exist in the current system. In addition, 4 decomposition pathways have been explored. Results show that the H 2 O 2 * will first undergo an O-H bond break (HOO*+H*), then the HO-O bond decomposes into H*+HO*+O* (Pathway (b)). By considering the concentration and activation energy together, the H 2 O*+O* is proposed to be the most possible active species for oxidative desulfurization due to the relative higher concentration and lower activation energy. [ABSTRACT FROM AUTHOR]

The pore structure of carbon materials strongly influences the electrochemical performance of carbon electrodes. Thus, carbon material pore structure modification methods need to be further explored to improve carbon electrode performance. In this work, fulvic acid is used as a carbon precursor to prepare oxygen-rich hierarchical porous carbon (OAHPC) by H 2 O 2 oxidation followed by synergistic activation with KOH. H 2 O 2 oxidation significantly increases the oxygen functional groups on the surface of the fulvic acid, which helps coordinate the KOH activation process. The prepared OAHPC has a mesopore ratio of 67.77%, a specific surface area (SSA) of 3362 m2·g−1, a total pore volume of 2.23 cm3·g−1, and an oxygen content of 34.01 wt%. The OAHPC is used as a supercapacitor electrode material in a three-electrode system. This OAHPC electrode displays a high specific capacitance of 453 F·g−1 at 0.2 A·g−1 in 6 M KOH as well as outstanding cyclic stability (86.8% capacitance retention after 5000 cycles). This method provides a new strategy for adjusting the pore structure of porous carbon materials. [Display omitted] • OAHPC is prepared from fulvic acid by H 2 O 2 oxidation followed by synergistic activation with KOH. • H 2 O 2 oxidation significantly increases the oxygen functional groups and optimizes the porous structure. • High specific surface area of 3362 m2·g−1. • Superior rate capability of 453 F·g−1 at 0.2 A·g−1. [ABSTRACT FROM AUTHOR]

CXCL8 is a typical CXC-type chemokine, which mediates the migration of immune cells from blood vessels to the site of inflammation or injury to clear pathogenic microorganisms and repair damaged tissues. In this study, Megalobrama amblycephala CXCL8 (MaCXCL8) gene was identified and characterized. Sequence analysis showed that the deduced MaCXCL8 protein possessed the typical structure of CXCL8 from other species, with the characteristic CXC cysteine residues in the N-terminal and accompanied by a DLR motif (Asp-Leu-Arg motif). Phylogenetic analysis revealed that MaCXCL8 was homologous to that of Ctenopharyngodon idella and other cyprinid fishes. MaCXCL8 gene was expressed in all detected healthy tissues, with the highest expression levels in the spleen, and its expression was significantly up-regulated upon the challenge of Aeromonas hydrophila and Lipopolysaccharide (LPS) both in juvenile M. amblycephala tissues and primary macrophages. The immunohistochemical assay showed that MaCXCL8 was mainly distributed in the nucleus and cytoplasm, and its expression levels increased observably with the prolongation of bacterial infection. In addition, recombinant MaCXCL8 protein exhibited significant chemotactic effects on neutrophils and macrophages. In conclusion, MaCXCL8 is involved in the immune response of M. amblycephala , and these findings will be helpful to understand the biological roles of MaCXCL8 and provide a theoretical basis for the prevention and control of fish bacterial diseases. • MaCXCL8 shared structural similarities with that of other teleosts, except DLR motif was in place of ELR-like motif. • The expression of MaCXCL8 was the most abundant in the spleen, which was dramatically increased upon bacterial infection. • LPS and Aeromonas hydrophila treatment significantly induced the up-regulation of MaCXCL8 expression in macrophages. • Recombinant MaCXCL8 protein exhibited chemotactic effects on neutrophils and macrophages. [ABSTRACT FROM AUTHOR]

To obtain the adsorption strength is the key point for materials design and parameters optimization in chemical engineering. Here we report a simple but accuracy method to estimate the adsorptive energies by counting the number of π-orbital involved atoms based on theoretical computations for hexagonal boron nitride (h-BN) and graphene. Computational results by density function theory (DFT) as well as spin-component scaled second-order Møller-Plesset perturbation theory (SCS-MP2) both confirm that the adsorptive energies correlate well with the number of π-orbital involved atoms for π-orbital contained molecules. The selected molecules (adsorbates) are commonly used in chemical industry, which contains C, N, S, O atoms. The predicted results for the proposed formulas agree well with the current and previous DFT calculated values both on h-BN and graphene surfaces. Further, it can be also used to predict the adsorptive energies for small π-orbital contained molecules on BN and carbon nanotubes. The interaction type for these adsorptions is typical π-π interaction. Further investigations show that the physical origin of these interactions source from the polar interactions between the adsorbents and adsorbates. Hence, for separation or removal of aromatic molecules, how to modify the aromaticity and polarity of both adsorbents and adsorbates will be the key points for experiments. [ABSTRACT FROM AUTHOR]

We have systematically investigated the electronic structures and magnetic properties of nonmetal doped MoSe 2 monolayer by using spin-polarized density functional theory calculations. Formation energies reveal that all doped systems are thermodynamically preferred under Mo-rich conditions than Se-rich conditions, and the incorporation of O atom into MoSe 2 monolayer is most favorable. Electronic structure analysis elucidates that Cl, Br and I doped systems exhibit half-metallic properties, while the band gap has been significantly tuned by H, B, C, N, and F doping. More importantly, H, B, N, F, Cl, Br, and I doping can induce pronounced magnetic moments in host MoSe 2 monolayer. [ABSTRACT FROM AUTHOR]

Entirely oligosaccharide-based supramolecular amphiphiles were constructed via host–guest interactions between ferrocene-terminated acetylated-maltoheptaose (Fc-AcMH) and β-cyclodextrin-terminated four-arm star maltoheptaose (MH4-β-CD). The amphiphiles could self-assemble to form spherical supramolecular nanoparticles to provide efficient drug delivery platforms. The combination of a pH-sensitive covalent acetal group and the oxidation-sensitive noncovalent host–guest interaction of β-CD and ferrocene provided the obtained fully oligosaccharide-based supramolecular amphiphiles. The structures of these amphiphiles could respond to the intracellular microenvironment. [ABSTRACT FROM AUTHOR]

An efficient two-level spatial uniform grid structure-based high-quality surface reconstruction method with Marching Cubes (MC) for smoothed particle hydrodynamics (SPH) fluids was presented in this paper. Compared with the traditional way that dividing the simulation domain with uniform grid directly, an enhanced narrow-band approach using the parallel cuckoo hashing method was taken to index the coarse-level surface vertices, hence decrease the memory consumption. Moreover, a two-level spatial uniform grid structure was employed with a scheme of arranging the fine surface vertices, which could preserve the spatial locality property to facilitate the coalesced memory access on the GPU. Our algorithm was designed for parallel architectures, based on which a parallel version of the optimized surface reconstruction was performed on the CUDA platform. In the experiment of comparison to traditional approaches, the results indicated that our surface reconstruction method was more efficient at the same level of quality of the reconstructed surfaces. [ABSTRACT FROM AUTHOR]

One central material issue in spintronics is the search for high temperature (above room temperature) magnetic semiconductors. We report on the formation of a transparent magnetic semiconductor with embedded ferromagnetic metallic glass nano-granules, showing a Curie temperature of ~ 600 K. Soft X-ray magnetic circular dichroism data verify its intrinsic room-temperature ferromagnetism. Owing to the unique structure of ferromagnetic nano-granules embedded in the host magnetic semiconductor, additional interfacial exchange anisotropy emerges and stabilizes the ferromagnetism. The magnetotransport measurements of the amorphous nanocomposite indicate that its anomalous Hall effect is dominated by the extrinsic mechanism of the side-jump due to the spin-dependent impurity. [ABSTRACT FROM AUTHOR]

This study focuses on an agricultural supply chain with a capital-constrained manufacturer, a bank and an insurer under three power structures: insurer-led Stackelberg (IS), bank-led Stackelberg (BS) and vertical Nash (VN). By establishing a two-level Stackelberg game, we examine the application condition and role of agricultural insurance under three channel structures and reveal the preferences of the supply chain and its participants for different channel structures. This study shows that, in either model, the manufacturer purchases agricultural insurance when the bank is highly loss-averse, but the probability of the manufacturer adopting agricultural insurance in the BS model is lower than that of the VN model but higher than that of the IS model. In these three models, the manufacturer's application of agricultural insurance increases the profits of the manufacturer, bank and insurer but reduces supply chain efficiency. In addition, from the perspective of the profit level and profit share of supply chain participants, for the manufacturer, the VN model of the two-level supply chain power structure betters than the BS and IS models of the three-level supply chain power structure, but the BS model is superior to the IS model; for the bank and the insurer, the higher their leadership positions in which power structure model, the better the power structure model. From the perspective of the overall profit and efficiency of the agricultural supply chain, the model preference of the supply chain is the same as that of the manufacturer. The findings provide new theoretical insights for the application of agricultural insurance and power relationship in the agricultural supply chain. • Application conditions and roles of agricultural insurance in IS, BS and VN models. • Profit relationship among the manufacturer, bank and insurer in IS, BS and VN models. • Preferences of the involved participants for different channel power structures. [ABSTRACT FROM AUTHOR]

We demonstrate the synthesis of SiOH-functionalized composite particles with buckled surface via a seeded emulsion polymerization method, their evolution into bicompartmental particles and their application in superhydrophobic coatings. By using polystyrene spheres swelled with non-polymerizable solvent as seeds, emulsion polymerization of 3-(trimethoxysily) propyl methacrylate and styrene leads to the formation of deflated ball- or dried plum-shaped composite particles. The change of solvent amount causes the variation of the morphologies of the obtained particles. With these composite particles as seeds for further emulsion polymerization, bicompartmental particles with unique morphologies are fabricated. On account of the silanol groups generated by hydrolysis of 3-methacryloxy propyl trimethoxysilane (MPS) on their surface, these particles are easily functionalized with organosilane for various applications and also could be applied in the synthesis of more complex organic-inorganic hybrid materials. The modification of the particles with fluorinated silane and their application in the fabrication of superhydrophobic surfaces are demonstrated. [ABSTRACT FROM AUTHOR]

Traditional enzyme-prodrug therapy (EPT) is a two-step strategy, which has many serious deficiencies, so having a one-step EPT treatment becomes a problem of immediate interest. This study aims to achieve an effective co-delivery of horseradish peroxidase (HRP) as a kind of enzyme for prodrug activation and ethyl 3-indoleacetate (EIA) as anticancer prodrug. A ternary block copolymer PEG-PAsp(AED)-CA consisting of poly(ethylene glycol) (PEG), reduction-sensitive poly ( N-(2,2′-dithiobis(ethylamine)) aspartamide) PAsp(AED), and cholic acid (CA) was synthesized and assembled into spherical micelles which encapsulated EIA in its hydrophobic core and HRP in a reduction-sensitive interlayer. TEM photographs show that the polymer micelle is around 40 nm, and the cell survival rate test shows that the EIA/HRP polymer micelle is highly lethal to human lung adenocarcinoma cells. Thus, co-delivery of EIA and HRP demonstrates great potential in cancer therapy, offering a structurally simple and highly tunable platform for the synchronous delivery of enzymes and prodrugs in EPT. [ABSTRACT FROM AUTHOR]

• Mechanism of CO2 adsorption on biomass derived carbon was explained using DFT methods. • Building the relationship between nucleophilicity and adsorption capacity of biochar. • Carboxyl and diketone groups are the most active O-containing sites. • TG-MS experiments proved the effect of nucleophilicity group of biochar on CO 2 adsorption. CO 2 adsorption is an important issue for sustainable development today. In this study, zigzag edge and armchair edge cluster models containing oxygen-containing groups were established, and the interaction with CO 2 molecules was calculated based on Density functional theory. The results indicated that the carboxyl and diketone groups have the CO2 adsorption capacity. The relationship between CO 2 adsorption performance and nucleophilicity of O-containing groups was established. A subsequent TG-MS experiment also proved that the introduction of nucleophilic group can promote interaction between CO 2 and carbon surface. [ABSTRACT FROM AUTHOR]

Two hexacyanoferrate-based , [C4Py]3Fe(CN)6 and [C16Py]3Fe(CN)6, were synthesized and characterized using Fourier transform infrared and mass spectroscopies and CHN analysis. They were employed as Fenton-like catalysts in extraction and catalytic oxidative of model oil with dibenzothiophene (DBT), benzothiophene (BT), 4,6-dimethyldibenzothiophene (4,6-DMDBT), 4-methyldibenzothiophene (4-MDBT) and 3-methylbenzothiophene (3-MBT) as substrates. Various polar solvents, such as , water and organic solvents, were applied to choose a suitable extractant. The results showed the removal of DBT reached 97.1% with [C4Py]3Fe(CN)6 as a catalyst and 1- n-octyl-3-methylimidazolium hexafluorophosphate ([C8mim]PF6) as an extractant under optimal conditions. The activity of followed the order DBT > 3-MBT > BT > 4-MDBT >4,6-DMDBT. The effect of water content on was investigated by adding various concentrations of H2O2. It was found that excess water had a positive effect on but the catalysts were less sensitive than [FeCl4−]-based catalysts to water. The mechanism was studied using electron spin-resonance spectroscopy and gas chromatography-mass spectrometry. O2•− may be the active oxygen species in the catalytic oxidative process and the oxidation products of various were the corresponding sulfoxides and sulfones. Copyright © 2016 John Wiley & Sons, Ltd. [ABSTRACT FROM AUTHOR]

Using density functional theory calculations, we have systematically explored the effect of V, Nb and Ta impurities on the electronic transport properties of 2 H -WSe 2 . The formation energies elucidate dopants are preferred to substitute W atoms, and the incorporation of Nb into WSe 2 is most thermodynamically favorable. The crystal structures almost hold the pristine WSe 2 structure-type in spite of with slightly bond relaxation. More importantly, a pronounced electronic transport behavior has realized in all doped systems, which is mainly triggered by metal impurities. Our calculation suggests chemical doping is an effective way to precisely modulate WSe 2 performance for target technological applications. [ABSTRACT FROM AUTHOR]

[Display omitted] • The species which Al atom anchoring on B site of h-BN is more stable. • The Al_edge_B 1 and Al_edge_B 2 species is more stable than other forms for Al-BN-SAAs. • All Al-BN-SAAs have superior ADS performance than pristine h-BN. • The enhanced performance is attributed to the newly formed S Al coordination bond. A concept of single atom adsorbents (SAAs) is proposed to the fields of highly selective adsorption desulfurization from diesel. Here, SAAs with the Al atom anchoring on the surface of hexagonal boron nitride have been systematically explored by density functional theory. Firstly, all the possible doping sites have been considered and their stabilities have been discussed by the doped energy. Additionally, the activity and selectivity for the adsorptive desulfurization of these Al-based SAAs have been predicted. Results show that all the Al-based SAAs can enhance the activity and selectivity of adsorptive desulfurization due to the newly formed S-Al coordination bond. We hope this work can provide a reliable theoretical foundation for the design of SAAs with higher adsorptive activity and superior selectivity. [ABSTRACT FROM AUTHOR]

• Numerical loaded tooth contact analysis for meshing interface. • Meshing interface state evolution under TEHL condition. • Non-Newtonian fluid ETHL model considering entrainment angle. • Separation flow method for the friction coefficient determination. • Energy loss and mechanical efficiency forecasting model. Energy loss and mechanical efficiency directly affect the service performance and reliability of aero-engine bevel gear power transmission, but there is currently a lack of effective diagnosis in early design stage due to the complex tooth meshing interface state evolution under the thermal elastohydrodynamic lubrication (TEHL) condition. A new energy loss and mechanical efficiency prediction model is proposed by using the improved TEHL analysis considering the entrainment angle and non-Newtonian fluid effect. Firstly, numerical loaded tooth contact analysis (NLTCA) is developed to determine tooth meshing kinematic relating to the entrainment and sliding states. Then, the entrainment angle is taken into account the Non-Newtonian fluid TEHL model and separation flow method is applied for friction coefficient solution. Finally, new energy loss and mechanical efficiency model is established by simulating the complex tooth meshing interface TEHL. This model is enabling ever-higher levels of aero-engine bevel gear production efficiency and design sustainability. It can provide an important access to geometric and physical assessments that can improve the energy generation, conversion, transfer and utilization of the whole aero-engine power transmission system. [Display omitted]. [ABSTRACT FROM AUTHOR]

H. P. Li and A. Sun performed the calculations and wrote the paper. Z. Y. Zhang and B. C. Guo carried out the draft preparation, H. B. Ji discussed the results. Y. Tian directed the entire study. All authors read and commented on the paper. [Display omitted] • CeCu 3 Co 4 O 12 is an antiferromagnetic semiconductor. • The chemical combination is confirmed to be Ce4+Cu2.67+ 3 Co3+ 4 O2- 12. • The magnetic interaction generates from the A-type antiferromagnetic coupling of A′-site Cu. • The B-site Co3+ with 3d6 (t 2g 6e g 0) electronic configuration is nonmagnetic in the low-spin state. We used the first-principles calculations to investigate the magnetic structure and electronic properties of quadruple perovskite CeCu 3 Co 4 O 12. Our calculations demonstrate that CeCu 3 Co 4 O 12 is an antiferromagnetic semiconductor, in which the A′-site Cu plays a decisive role in magnetic properties. The chemical combination is proved to be Ce4+Cu2.67+ 3 Co3+ 4 O2- 12. The mixed-valence Cu2.67+ at A′-site shows A-type antiferromagnetic coupling, whereas the B-site Co3+ with 3d6 (t 2g 6e g 0) electronic configuration is nonmagnetic in the low-spin state. Moreover, the spin-orbital coupling (SOC) effect does not alter the semiconducting performance of CeCu 3 Co 4 O 12 , although the bandgap is sharply reduced when SOC effect was taken into consideration. [ABSTRACT FROM AUTHOR]

Deep eutectic solvents (DESs), as ionic liquid analogues for green solvents, have gained increasing attentions in chemistry. In this work, three typical kinds of DESs (ChCl/Gly, ChCl/AcOH and ChCl/Urea) were successfully synthesized and characterized by Fourier transform infrared spectroscopy (FTIR) and Raman. Then comprehensive and systematical analyses were performed by the methods of density functional theory (DFT). Two methods (B3LYP/6-311 + +G(2d,p) and dispersion-corrected B3LYP-D3/6-311 + +G(2d,p)) were employed to investigate the structures, vibrational frequencies and assign their ownership of vibrational modes for the DESs, respectively. Nearly all the experimental characteristic peaks of IR and Raman were identified according to the calculated results. By linear fitting of the combined calculated vs experimental vibration frequencies, it can be found that both of the two methods are excellent to reproduce the experimental results. Besides, hydrogen bonds were proved to exist in DESs by IR spectrum, structure analysis and RDG analysis. This work was aimed at predicting and understanding the vibrational spectra of the three typical DESs based on DFT methods. Moreover, by comparing experimental and theoretical results, it provides us a deep understanding of the formation mechanisms of DESs. [ABSTRACT FROM AUTHOR]

We perform a first-principles study of electronic structure and magnetic properties of V, Nb and Ta-doped WS 2 monolayers. Formation energy calculations reveal that all the doped systems are thermodynamically more preferred under S-rich condition than W-rich condition, and that under either condition the incorporation of 5d Ta dopant into monolayer is the most favorable, followed by the incorporation of 4d Nb and 3d V. Electronic structure analysis reveals that all the doped systems show p-type doping and metallic character, i.e. metallicity in the V-doped case, while half-metallicity in the Nb and Ta-doped cases. Furthermore, ferromagnetism is induced by the impurities, which mainly comes from the coupling between unpaired d orbitals of the dopants and the nearest neighbors of W 5d and S 3p states. These findings indicate that doping metals in WS 2 monolayers may act as a useful way to tailor the electronic structure of two-dimensional materials for many device applications. [ABSTRACT FROM AUTHOR]

Chemical doping represents one of the most effective ways in engineering electronic structures of anatase TiO2 for practical applications. Here, we investigate formation energies, geometrical structures, and electronic properties of Si-, F-doped and Si/F co-doped anatase TiO2 by using spin-polarized density functional theory calculation. We find that the co-doped TiO2 is thermodynamically more favorable than the Si- and F-doped TiO2- Structural analysis shows that atomic impurity varies crystal constants slightly. Moreover, all the three doped systems show a pronounced narrowing of band gap by 0.33 eV for the F-doped TiO2, 0.17 eV for the Si-doped TiO2, and 0.28 eV for the Si/F-co-doped TiO2, which could account for the experimentally observed redshift of optical absorption edge. Our calculations suggest that the Si/F-co-doping represents an effective way in tailoring electronic structure and optical properties of anatase TiO2. [ABSTRACT FROM AUTHOR]

In this work, interaction nature between a group of aromatic sulfur compounds and [BMIM] + [FeCl 4 ] − have been investigated by density functional theory (DFT). A coordination structure is found to be critical to the mechanism of extractive desulfurization. Interaction energy and extractive selectivity follow the order: thiophene (TH) < dibenzothiophene (DBT) ≈ benzothiophene (BT). Alkylation of TH or BT ( e.g. 3-methylthiophene, and 3-methylbenzothiophene) leads to a stronger interaction with ionic liquid, but steric hindrance effects of some alkylic derivatives ( e.g. 2,7-dimethylbenzothiophene) lead to a weaker interaction with ionic liquid. The mechanism of extractive desulfurization is attributed to the charge transfer effect. During extractive desulfurization, electrons on aromatic sulfur compounds transfer into the Lewis part of ionic liquid, namely, [FeCl 4 ] − . Furthermore, it is better to consider the Lewis acidity of Fe-containing ionic liquid by the whole unit (such as [FeCl 4 ] − and aromatic sulfur compounds (X)) rather than only Fe or S atom. [ABSTRACT FROM AUTHOR]