Search

CD68 is a highly glycosylated transmembrane glycoprotein that belongs to the lysosome-associated membrane glycoprotein family and is involved in various immune processes. In this study, Megalobrama amblycephala CD68 (MaCD68) was cloned and characterized, and its expression patterns and evolutionary characteristics were analyzed. The coding region of MaCD68 was 987 bp, encoding 328 amino acids, and the predicted protein molecular weight was 34.9 kDa. MaCD68 contained two transmembrane helical structures and 18 predicted N-glycosylation sites. Multiple sequence alignments showed that the MaCD68 protein had high homology with other fish, and their functional sites were also highly conserved. Phylogenetic analysis revealed that MaCD68 and other cypriniformes fish clustered into one branch. Adaptive evolution analysis identified several positively selected sites of teleost CD68 using site and branch-site models, indicating that it was under positive selection pressure during evolution. Quantitative real-time reverse transcription polymerase chain reaction analysis showed that MaCD68 was highly expressed in the head kidney, spleen, and heart. After Aeromonas hydrophila infection, MaCD68 was significantly upregulated in all tested tissues, peaking at 12 h post-infection (hpi) in the kidney and head kidney and at 120 hpi in the liver and spleen, suggesting that MaCD68 participated in the innate immune response of the host against bacterial infection. Immunohistochemical and immunofluorescence analyses also showed that positive signals derived from the MaCD68 protein were further enhanced after bacterial and lipopolysaccharide treatment, which suggested that MaCD68 is involved in the immune response and could be used as a macrophage marker. Biological activity analysis indicated that recombinant MaCD68 (rMaCD68) protein had no agglutination or bactericidal effects on A. hydrophila but did have these effects on Escherichia coli. In conclusion, these results suggest that MaCD68 plays a vital role in the immune response against pathogens, which is helpful in understanding the immune responses and mechanisms of M. amblycephala. [ABSTRACT FROM AUTHOR]

[Display omitted] • The hydroxylation of anhydrous phosphogypsum (APG) significantly improved the grafting rate of the modifier. • The modified APG (M-APG) has certain hydrophobic properties. • Appropriate filling of M-APG can improve the mechanical properties of PP. • The functional mechanism of PG surface hydroxylation and modification was clarified. Phosphogypsum (PG) is a solid waste residue in the production of phosphoric acid by the wet process, and many deposits of this waste pollute the environment. Anhydrous Phosphogypsum (APG) was prepared by pretreatment of PG, after which its surface was hydroxylated by NaOH solution. The surface hydrophobic modification of APG was achieved by grafting 3-(methacryloxy)propyltrimethoxysilane (KH570), alkoxytri (dioctyl pyrophosphate acyloxy) titanate (TCA-L38), and stearic acid (SA), respectively, on hydroxylated APG surfaces. The chemical surface structure and properties of the APG materials were determined, and the mechanism of the hydrophobic surface modification was discussed. Finally, the modified APG was used as polypropylene (PP) filler to prepare PP composites by melt blending. The results showed that the hydroxyl content on the surface of APG was significantly increased after hydroxylation, which significantly increased the grafting rate of KH570, SA, and TCA-L38 on the surface of APG. KH570, SA, and TCA-L38 could react with the hydroxyl group of APG, which were closely adsorbed on the surface of APG by chemical adsorption. The water contact angles of APG-OH-KH570, APG-OH-SA, and APG-OH-TCA were 80.52°, 124.99°, and 123.77°, respectively. The surface hydroxylation and hydrophobic modification of APG significantly improved the compatibility and interfacial interaction between APG and PP. The mechanical properties APG-OH-KH570/PP, APG-OH-TCA/PP, and APG-OH-SA/PP composites were better than those of pure PP. [ABSTRACT FROM AUTHOR]

The fabrication of graphitic carbon nitride (g-C 3 N 4) has received much attention for its superior photoelectronic properties, it remains a remarkable challenge with a feasible methodology. Herein, inspired by carburization, a novel method with carbon diffusion was proposed to prepare g-C 3 N 4 nanosheets (CNNS). The carbon diffusion was caused by the gradient difference in carbon concentration between the gaseous environment and the C15 (mild steel with low carbon content) during thermal polymerization. Eventually, the CNNS with approximately 1.5 nm thickness was successfully fabricated and exhibited larger surface area (98.08 m2 g−1), which was 15.42 times higher than that of bulk g-C 3 N 4 (BCN). In the evaluation of photocatalytic CO 2 reduction activity, the CH 3 OH formation rate over CNNS (2.10 μmol g−1 h−1) was 3.28 times greater than BCN. Meanwhile, the designed CNNS exhibited dramatic improvement on H 2 evolved rate (HER) of 2507.02 μmol g−1 h−1, which was 6.99 times higher than BCN. More importantly, the C15 possessed the advantage of 10 times recycled to use for the fabrication of CNNS accompanied by a moderate decrease of HER. Moreover, the density functional theory (DFT) calculations were carried out based on the results. This work highlights an ingenious tactic with carbon diffusion for preparing CNNS towards renewable solar energy conversion. Herein, we reported an inducing carbon diffusion strategy for fabricating g-C 3 N 4 nanosheets to realize effectively solar energy conversion. [Display omitted] [ABSTRACT FROM AUTHOR]

Improving the tribological performance of carbon fabric (CF)/polymer composites is vitally significant for developing high‐performance lubricating materials. We propose the combination of interfacial modification and use of a lubricant additive to enhance the antifriction and anti‐wear properties of CF/phenolic (PF) composites. And the tribological properties of CF/PF composites were characterized using ball‐on‐disc friction and wear tester. First, ZnO nanorods were densely and uniformly grown on the carbon fiber surface using POSS as a "bridge molecule" to make fiber with a rough micro‐nano microstructure and active functional groups; this was conducive to enhancing the interlaminar shear strength (ILSS) and wear resistance of CF/PF. Then, graphite (Gr) was further introduced as a lubrication additive into the modified CF‐POSS‐ZnO/PF to increase the friction‐reducing capacity. The corresponding modified composite with 5 wt% Gr demonstrated outstanding tribological performance. The coefficient of friction and wear rate decreased by 55.37% and 93.36%, respectively, compared to those of CF/PF. Moreover, it still retained outstanding friction and wear properties in the sliding process with high loads and speeds. The synergistic mechanism of interfacial modification and lubricant additive on the tribological performance of CF/PF are discussed systematically on the basis of the analysis of the ILSS, fracture surface microstructures, and worn surfaces of the composites. This work might shed new light on the design and development of high antifriction and anti‐wear CF/polymer composites. [ABSTRACT FROM AUTHOR]

Dual–single‐atom catalysts with synergistic effect of adjacent atomic metal sites show a great potential for oxygen reduction reaction (ORR). Herein, a dynamical synthetic strategy is demonstrated for the rational design of dual‐atom catalyst ((Zn, Cu)−NC) with non‐covalent Cu and Zn sites as nitrogen‐doped carbon as support. Owing to the non‐covalent interaction of Zn and Cu atomic pair sites, (Zn, Cu)−NC exhibits significant performances for ORR, surpassing the catalysts with individual Zn or Cu site. The theoretical calculations reveal that (Zn, Cu)−NC can highly activate the linear O2 molecule via the non‐covalent interaction between Zn and Cu pairs, providing the more effective overlap between the metal 3d orbitals and O 2p orbital. Therefore, the ORR activity is optimized with the improvement of the adsorption configuration and adsorption energy of O2. Further, both liquid and quasi‐solid zinc−air batteries with (Zn, Cu)−NC as air cathodes achieve remarkable energy density and stability. This research proposes a facile synthetic strategy to construct single‐atom catalysts and presents an insightful understanding of the non‐covalent interplay between heteronuclear metal atoms in dual‐atom catalysts. [ABSTRACT FROM AUTHOR]

[Display omitted] • UiO-66-BAPILs were designed and fabricated for oxidative desulfurization. • The permanent cavity in UiO-66-BAPILs was validated by gas uptake experiments and molecular size simulations. • UiO-66-BAPILs exhibited higher catalytic activity than the two components. • The mechanism was in detail studied by experiments and theoretical calculations. Porous ionic liquids have been highlighted with special interest for their desirable catalytic activity and extraction properties. Herein, bifunctional porous ionic liquids (denoted UiO-66-BAPILs) were synthesized by dispersing UiO-66 into a pyridinium-based Brønsted acidic ionic liquid ([BSPy][CF 3 SO 3 ]) for oxidative desulfurization. The permanent cavity of UiO-66 moiety in UiO-66-BAPILs was validated as well-preserved by the SO 2 uptake experiments and molecular size simulations. Under the optimum reaction conditions, the sulfur removal could reach up to 99.5% with hydrogen peroxide as the oxidant. Additionally, bifunctional UiO-66-BAPILs were deemed as both extractants and catalysts during the reaction. A possible mechanism has been proposed that UiO-66-BAPILs extract the aromatic sulfur compounds via π···π interactions and C-H···π interactions and meanwhile oxidize them with peroxysulfonic acids and •OH radicals. These findings will open up new avenues to facilitate the catalytic oxidation performance by constructing bifunctional Brønsted acidic porous ionic liquids. [ABSTRACT FROM AUTHOR]

A bifunctional guanidine-functionalized basic binuclear poly(ionic liquid)s were successfully prepared ternary copolymerization of binuclear bromine ILs, guanidine functionalized binuclear ILs and DVB by free radical polymerization, which were applied for one-pot efficiently catalyzing the cycloaddition of the simulated flue gas (15% CO 2 + 85% N 2) without any co-catalyst. [Display omitted] • Novel guanidine-functionalized basic binuclear poly(ionic liquid)s (GB-PILs) are successfully prepared. • GB-PILs provide the built abundant pores and the exposed bromine anions. • GB-PILs can efficiently catalyze the CO 2 cycloaddition of the simulated flue gas without solvent and cocatalyst. • The mechanism of co-catalyzing the cycloaddition reaction of CO 2 and epoxide with guanidine basic sites and binuclear ones in P-DBTMGH catalyst is explored. The direct conversion of low partial pressure (10–15 %) from industrial waste gas into high value-added chemicals provides a favorable solution to global climate change. However, developing high-efficient catalysts for the conversion of low partial pressure CO 2 under mild conditions is still a major challenge. Here, guanidine-functionalized basic binuclear poly(ionic liquid)s (P-DBTMGH) were prepared by free radical copolymerization. With the introduction of guanidine ionic liquids into the framework of GB-PILs, the alkalinity in the structure was improved, and thus enhancing CO 2 surface adsorption and activation ability. Meanwhile, bromide containing binuclear sites help to increase the ion density of bromide and promote the occurrence of ring opening. Using epichlorohydrin as a probe substrate, P-DBTMGH could efficiently catalyze the cycloaddition reaction of the simulated flue gas (15 vol% CO 2 + 85 vol% N 2) without any co-catalyst or solvent, and chloropropene carbonate (CPC) with a selectivity and yield of 99 % and 96 % was obtained, which was better than or equivalent to the results reported previously. Moreover, the theoretical studies deeply understood the synergetic effect of guanidine basic sites and bromide containing binuclear sites on CO 2 activation and ring-opening of epoxides, which provides a better choice for high-value utilization of low partial pressure CO 2 from flue gas. [ABSTRACT FROM AUTHOR]

[Display omitted] • The carbon quantum dot is employed as cocatalyst to boost the catalytic oxidative desulfurization of phosphotungstic acid ionic liquid. • The carbon quantum dot favors the activation of hydrogen peroxide. • The CQDs/C 18 PWIL-1 exhibits excellent desulfurization efficiency under ambient conditions, in which dibenzothiophene was completely removed within 30 min. SO x emission from fossil fuel combustion is an important reason for environmental pollution. Achieving deep removal of sulfur-containing compounds from the fuel is essential. Herein, by combining phosphotungstic acid (HPW) with ionic liquids (ILs) and incorporating carbon quantum dots (CQDs), a series of catalysts (CQD/C 18 PWIL-x) for oxidative desulfurization (ODS) are prepared. Experimental results reveal that the modification of ILs could facilitate full contact between the active site and the organic phase, and improve mass transfer in the oxidative desulfurization process. Moreover, the incorporation of CQDs can promote the utilization of hydrogen peroxide. The synergistic action of multiple components leads to better activation of hydrogen peroxide. Therefore, the CQDs/C 18 PWIL-1 exhibits excellent desulfurization efficiency under ambient conditions, in which dibenzothiophene was completely removed within 30 min. Meanwhile, as heterogeneous catalyst, CQDs/C 18 PWIL-1 shows excellent cycling stability. The direct incorporation of CQDs significantly improves the catalytic activity and provides a new inspiration for the application of CQDs to ODS processes. [ABSTRACT FROM AUTHOR]

For hypoid gear transmission showing time-varying meshing characteristics, three always is a very complicated solid-liquid-thermo-mechanical coupling lubrication interface behavior. In full consideration of tooth flank roughness and non-Newton fluid effect for this thermal elastohydrodynamic lubrication (TEHL) interface, an innovative multi-field coupling lubrication interface heat transfer model is established. Firstly, dynamic loaded tooth contact analysis (DLTCA) is performed to determine the input parameters about lubrication interface behavior, such as meshing interface kinematics, load distribution and entrainment speed parameters. Then, considering tooth roughness setup and non-Newton fluid flow, accurate TEHL interface heat transfer model is developed by establishing three-dimensional (3D) energy equation. Moreover, heat transfer model is solved for time-varying TEHL assessments including oil film pressure, temperature and thickness. Where, a non-Newton fluid effect correction is used to get accurate discretization of oil film pressure flow. In accurate solution to non-Newton fluid effect, an improved Eyring rheological model is employed for accurate computation of comprehensive shear force, flow factor and equivalent viscosity. A column-by-column scanning method is applied to determine the temperature field in a given computational domain. Finally, the numerical instances are provided to verify the proposed model. • DLTCA for basic input parameters determination; • TEHL governing equation considering tooth flank roughness and non-Newton fluid effect; • Computation for roughness tooth flank non-Newton TEHL forecasting equation; • Roughness tooth flank non-Newton TEHL forecasting model; • Time-varying characteristics of TEHL assessments [ABSTRACT FROM AUTHOR]

Lignin is a vital organic constituent of plant biomass and it can be transformed into value-added chemicals through chemical processes. This study employs the Density Functional Theory (DFT) to investigate the mechanistic effects of various oxidants on the depolymerization of sodium lignosulfonate model compounds into vanillin. Under alkaline conditions, OH- ions participation in the hydrolysis of β-O-4 bonds has been predicted. The dehydration of dihydroconiferyl alcohol to form eugenol, with an energy barrier of 69.0 kcal/mol was identified as the major rate-determining step in the oxidation reaction. In the absence of an oxidant, the energy barrier for the oxidation of eugenol to vanillin was 77.8 kcal/mol. However, when using nitrobenzene or H 2 O 2 as oxidants, the energy barrier has significantly decreased to 12.6 kcal/mol and 21.4 kcal/mol, respectively. The effects of temperature and pressure on the rate-determining step of the reaction were analyzed using Statistical Product and Service Solutions (SPSS) software. These results have demonstrated that the energy barrier for the hydrolysis reaction's rate-determining step is positively correlated with temperature but negatively correlated with pressure. These theoretical findings would potentially help in designing the experiments and aid in enhancing the selectivity and yield of vanillin. [Display omitted] • OH- ions promote the breaking of β-O-4 bonds. • Using oxidants like nitrobenzene or H 2 O 2 reduces energy barrier. • Nitrobenzene oxidizes isoeugenol to vanillin with lower energy barrier. [ABSTRACT FROM AUTHOR]

Based on the acid–base neutralization, the (1-methylimidazolium)(tetrazol-1-yl)borane was successfully synthesized by taking advantage of the acidity of the tetrazole and the basicity of the 1-methylimidazole borane complex. Through HRMS, NMR, and FT−IR, the structure of synthetic compounds was characterized in detail. Concerning about the (1-methylimidazolium)(tetrazol-1-yl)borane, it had an ignition−delay time of about 25 ms and a density specific impulse over 351 s·g/cm3, making it a suitable candidate for green hypergolic fuels. Moreover, it also demonstrated that introducing tetrazole into the borane could be an appropriate strategy to adjust the performance of the energy of those borane compounds. [ABSTRACT FROM AUTHOR]

Single atom adsorbents (SAAs) are a novel class of materials that have great potential in various fields, especially in the field of adsorptive desulfurization. However, it is still challenging to gain a fundamental understanding of the complicated behaviors on SAAs for adsorbing thiophenic compounds, such as 1-Benzothiophene (BT), Dibenzothiophene (DBT), and 4,6-Dimethyldibenzothiophene (4,6-DMDBT). Herein, we investigated the mechanisms of adsorptive desulfurization over a single Ag atom supported on defective hexagonal boron nitride nanosheets via density functional theory calculations. The Ag atom can be anchored onto three typical sites on the pristine h-BN, including the monoatomic defect vacancy (B-vacancy and N-vacancy) and the boron-nitrogen diatomic defect vacancy (B-N-divacancy). These three Ag-doped hexagonal boron nitride nanosheets all exhibit enhanced adsorption capacity for thiophenic compounds primarily by the S-Ag bond with π-π interaction maintaining. Furthermore, from the perspective of interaction energy, all three SAAs show a high selectivity to 4,6-DMDBT with the strong interaction energy (−33.9 kcal mol−1, −29.1 kcal mol−1, and −39.2 kcal mol−1, respectively). Notably, a little charge transfer demonstrated that the dominant driving force of such S-Ag bond is electrostatic interaction rather than coordination effect. These findings may shed light on the principles for modeling and designing high-performance and selective SAAs for adsorptive desulfurization. [ABSTRACT FROM AUTHOR]

The incomplete polymerization of graphite carbon nitride (g-C 3 N 4) due to the kinetic problems resulted in its high recombination rate of photo-generated electron-hole pairs. Hence, cyano-containing carbon nitride with coral-like morphology (CCCN) was prepared by the molten salt method with heptazine-based melem as precursor, which presented excellent separation rate of photo-generated electron-hole pairs. SEM exhibited that CCCN owned coral-like morphology which exposed ample active sites and enhanced the capture ability of visible light while FT-IR and XPS demonstrated that cyano groups appearing in coral-like carbon nitride enhanced the separation rate of photo-induced charge carriers. The synergistic effect of coral-like morphology and cyano groups endowed CCCN-15% with superior performance of both the photocatalytic H 2 evolution (4207 μmol h−1 g−1) and Cr (Ⅵ) reduction (k = 0.059 min−1), approximately 16.8 and 6.0 times that of g-C 3 N 4 , which was comparable among the similar materials. Density functional theory calculation (DFT) revealed that cyano groups decreased the bandgap and strengthened the activation degree of reaction substrate, which enhanced the thermodynamic driving force and the interaction between catalyst and substrate. This work provided a potential strategy for both the renewable energy generation and environmental restoration. • Cyano-containing carbon nitride with coral-like morphology (CCCN) was firstly prepared. • Coral-like morphology led to more active sites and stronger capture ability of visible light. • DFT revealed that cyano groups improved the thermodynamic driving force and interaction between catalyst and substrate. [ABSTRACT FROM AUTHOR]

FexOy@FexOy/C nanoparticles with a soap-bubble-like shell have been synthesized, and the materials exhibit excellent Fenton catalytic performance. More importantly, FexOy@FexOy/C nanoparticles as catalysts and precursors could catalyze organic dye molecules to form iron oxide@organic dye polymer core–shell nanospheres. [ABSTRACT FROM AUTHOR]

Five low-cost deep eutectic solvents (DESs) were synthesized based on choline chloride (ChCl) and a series of straight-chain monobasic acids. Under UV light irradiation, one-pot extraction combined with the metal-free photochemical aerobic oxidative deep desulfurization of fuels in deep eutectic solvents was successfully achieved. This liquid-liquid extraction and photochemical oxidative desulfurization system (EPODS) comprised of air, isobutylaldehyde (IBA), DESs and model oil. The factors influencing sulfur removal were systematically investigated, including the amount of DES, volume ratio of model oil and IBA, different sulfur concentrations, different substrates and fuel composition. The sulfur removal of dibenzothiphene (DBT) could reach 98.6% with air as oxidizing agent under UV light irradiation. Sulfur removal by different sulfur compounds decreased as BT ＞ DBT ＞ 4,6-DMDBT. The possible photochemical oxidative desulfurization mechanism was researched by gas chromatograph-mass spectrometer (GC-MS), electron spin-resonance (ESR) spectroscopy and density functional theory (DFT). [ABSTRACT FROM AUTHOR]

Metal-free graphene-like boron nitride (BN) samples were prepared and applied as adsorbents for removing dibenzothiophene (DBT) in model oil. The results showed that the graphene-like BN exhibited a remarkable adsorption performance. The adsorption capacity could reach 28.17 mg S g−1 adsorbent. Experiments have been carried out to investigate the effects of the number of BN layers, DBT initial concentration, and temperature on DBT adsorption. Langmuir and Freundlich isotherm models were used to study the adsorption of DBT on BN. The kinetic results showed that the adsorption process was best described by the pseudo-second-order kinetic model. Density functional theory (DFT) was employed to prove that the Lewis acid–base interaction plays an important role in removing DBT over graphene-like BN. [ABSTRACT FROM AUTHOR]

Extraction of aromatic sulfur compounds from model oil using a temperature-responsive ionic liquid (IL) N-butyl-N-methylpiperidinium tetrachloroferrate ([C 4 mpip]FeCl 4 ) as extractant has been investigated. In the extractive desulfurization process, liquid–liquid equilibrium was obtained at 45 °C for 10 min. After the extraction system was cooled to room temperature, the IL returned to solid due to the reversible thermoregulated phase transition of the IL. Therefore, it was easy for separation of oil and solid [C 4 mpip]FeCl 4 . The extraction efficiency and Nernst partition coefficient ( K N ) could get to 45.5% and 2.92, respectively, after a single extraction of DBT. Some important factors, such as extraction temperature, the amount of IL, initial sulfur content, multiple extractions, reusability and the mutual solution were investigated. The extraction ability of different sulfur compounds followed the order DBT > BT > 4,6-DMDBT. Finally, the extraction mechanism was studied systematically with experimental and theoretical methods. Compared with the extraction abilities of another three ILs, [C 8 mpip]FeCl 4 , [C 12 mpip]FeCl 4 and [C 4 Py]FeCl 4 , the size and aromatic structure of cation may be two positive factors but not the main extraction mechanism. The coordination interaction between Fe atom of IL and S atom of DBT was confirmed by IR spectra and theoretical computation. [ABSTRACT FROM AUTHOR]

Objective: Circulating tumor DNA (ctDNA) is emerging as a versatile biomarker for noninvasive genotyping and response monitoring in specific B‐cell lymphomas; however, few studies have been conducted to explore ctDNA‐based mutation profiling across non‐Hodgkin lymphomas (NHLs) and genomic changes after initiation of chemotherapy. Methods: A targeted sequencing of 362 genes was performed to detect the mutation profiles in paired blood and tissue samples from 42 NHL patients. Genomic alterations were explored in 11 diffuse large B‐cell lymphoma (DLBCL) patients using paired blood samples collected pre‐ and post‐R‐CHOP chemotherapy. Results: The frequencies of PIM1, MYD88, MYC, ZNF292, JAK, and MAF mutations were higher in aggressive than in indolent B‐cell lymphoma and NK/T subtypes. Tumor mutation burden in blood samples was higher in aggressive than in indolent B‐cell lymphomas and higher in patients who progressed than in those who responded to treatments. Our data also revealed significant enhance of concordance index through integrating mutated genes that were significantly associated with prognosis into International Prognostic Index‐based prognostic model. Moreover, acquisition of mutations such as PCLO_p.L1220Tfs*3 was associated with resistance to R‐CHOP in DLBCL patients. Conclusions: Our findings illustrated distinct mutation patterns across various NHL subtypes and suggested the association of genomic alterations in ctDNA with treatment outcomes. [ABSTRACT FROM AUTHOR]

Electrocatalytic reduction of CO2 over zeolitic imidazolate frameworks (ZIFs) generally has poor activity and low CO Faradaic efficiency due to the poor contact between conductive substrate and ZIFs synthesized by ex‐situ method. Here, ZIF‐8 films on Zn foils (ZIF‐8/Zn) fabricated by in‐situ electrochemical deposition were used for CO2 electroreduction in ionic liquid‐based ternary electrolyte. Tunable morphology and thickness of ZIF‐8 film can regulate the activity of CO2 electroreduction. The ZIF‐8/Zn‐40 electrode demonstrates the highest CO Faradaic efficiency (91.8 %) with the current density of 12.6 mA cm−2 at −1.9 V vs. Ag/Ag+, which is superior to the performance of ZIF‐8/CP electrode prepared by ex‐situ method. The excellent activity of ZIF‐8/Zn‐40 electrode is mainly attributed to abundant active sites in 3D structures with largest surface area, tight and good contact between ZIF‐8 film and Zn foil, faster rate CO2 diffusion, and synergistic effect between electrode and [Bmim]PF6‐containing electrolyte. The facile synthesis of ZIF‐8/Zn electrode provides a novel technology to design efficient electrodes for CO2 electroreduction. [ABSTRACT FROM AUTHOR]

Summary: In this study, oleic acid was used as a model compound to discuss the mechanism of thermal conversion of unsaturated fatty acids to hydrocarbons, so as to promote the goal of obtaining renewable chemicals and fuels from unsaturated fatty acids. In‐situ detection techniques such as TG‐FTIR and Py‐GC/MS combined with density functional theory were applied to study the reaction mechanism of oleic acid molecules in the conditions of slow pyrolysis and fast pyrolysis. As the temperature rises, the hydrogen bond is broken, and the vibration peak of oleic acid shows obvious dehydrogenation under slow pyrolysis, and the same situation exists under fast pyrolysis. As the temperature increases, the pyrolysis process of oleic acid molecules changed from the dominant role of bimolecular mutual catalysis to that of free radical reaction. The results of Py‐GC/MS showed that methyl, ethyl, and hydrogen radicals are the main active substances under the conditions of high temperature and fast pyrolysis of unsaturated fatty acid. This work demonstrates the feasibility of producing renewable hydrocarbons by pyrolysis of unsaturated fatty acids and proposed influenced factors to control product distribution. Novelty Statement: Density functional theory (DFT) combined with experiments was used in present study to supplement the understanding of the pyrolysis mechanism of fatty acids in bio oil pyrolysis, and the control factors of controlling the distribution of fatty acid pyrolysis products were proposed. [ABSTRACT FROM AUTHOR]

Construction of photocatalyst that combines excellent electron transfer and photoresponse capabilities to enhance photocatalytic performance remains a challenging task. In this work, interfacial Mo-N bonds and vacancy engineering collaborative modified MoO 3-x @polypyrrole (MP) S-scheme heterojunction is rational designed for efficient photocatalytic oxidative desulfurization. The addition of polypyrrole introduces rich defects which inducing the localized surface plasmon resonance (LSPR) effect and enhancing light absorption. Furthermore, the combination facilitates the formation of Mo-N bonds. The modifications amplify the built-in electric field and conduct the efficacious separation of photogenerated carriers. With the synergism of LSPR effect and interfacial chemical Mo-N bonds, the optimal MP photocatalyst displays attractive desulfurization rate of 100% for dibenzothiophene (DBT) in 60 min under illumination, touching the objective of ultra-deep desulfurization. The study extends a novel understanding of the impact of LSPR effect and heterojunction interface charge transfer on the photocatalytic desulfurization ability. [Display omitted] • S-scheme heterojunction MP with chemical coupling for DBT desulfurization is designed. • The increased OV concentration induces LSPR effect and enhance the light adsorption. • The formation of Mo-N bond enhances interface coupling as electron transfer channel. • e－ of MoO 3-x rapidly combines with h+ of PPy which enhance photocatatlytic ability. [ABSTRACT FROM AUTHOR]

This study employed the DFT method to calculate the catalytic activity of various organic functional groups during phenol production on seaweed biochar. It also used machine learning to analyze the correlation between electronic structure parameters of different sites and their catalytic activity. Finally, it summarized the essential characteristics of the most active site. [Display omitted] • Establishing cluster models of algal biochar catalyst and its catalytic mechanisms for lignin upgrading using a DFT method. • Decision trees, random forests, gradient boosting, and extreme gradient boosting were used to establish prediction models. • The random forest method performs best in revealing catalyst reactivity. • Fukui function is an effective descriptor for evaluating the reaction activity of adsorption sites. With the continuous development of the industrialization process, the reserves of primary energy sources such as petroleum have sharply decreased. The development of efficient and economical catalysts is of great significance in promoting the rapid pyrolysis of biomass to produce high-quality liquid fuels and chemicals. In this study, density functional theory (DFT) and machine learning (ML) were used to explore the catalytic reaction mechanism of guaiacol pyrolysis over seaweed biochar catalyst. Models of algae biochar catalysts with oxygen-containing or nitrogen-containing functional groups were established, and the surface transformation mechanism of guaiacol over the biochar catalyst was calculated using DFT. Furthermore, four machine learning methods (decision tree (DT), random forest (RF), gradient boosting (GB), and extreme gradient boosting (XGBoost)) were used to establish a mathematical model based on catalyst characteristics for predicting key intermediate adsorption energy during catalysis reaction. The fitting results and performance analysis of each prediction model show that the RF method-trained model has the highest accuracy. Fukui function (f-) was proved as an effective descriptor to evaluate the reactivity of adsorbed sites. This study provides a pathway to developing more efficient biochar catalysts, which could lead to more sustainable and environmentally friendly energy solutions. [ABSTRACT FROM AUTHOR]

By analyzing the variability of global SST (sea surface temperature) anomalies, we propose a unified Niño index using the surface thermal centroid anomaly of the region along the Pacific equator embraced by the 0.7°C contour line of the standard deviation of the SST anomalies and try to unify the traditional Niño regions into a single entity. The unified Niño region covers almost all of the traditional Niño regions. The anomaly time series of the averaged SST over this region are closely correlated to historical Niño indices. The anomaly time series of the zonal and meridional thermal centroid have close correlation with historical TNI (Trans-Niño index) indices, showing differences among El Niño (La Niña) events. The meridional centroid anomaly suggests that areas of maximum temperature anomaly are moving meridionally (although slightly) with synchronous zonal movement. The zonal centroid anomalies of the unified Niño region are found helpful in the classification of the Eastern Pacific (EP)/Central Pacific (CP) types of El Niño events. More importantly, the zonal centroid anomaly shows that warm areas might move during a single warming/cooling phase. All the current Niño indices can be well represented by a simple linear combination of unified Niño indices, which suggests that the thermal anomaly (SSTA) and thermal centroid location anomaly of the unified Niño region would yield a more complete image of each El Niño/La Niña event. [ABSTRACT FROM AUTHOR]

Gear tooth flank dry-cutting was beget with emergent and disruptive NC technology. This new technology is enabling ever-higher levels of production efficiency and sustainability. It also has the potential to dramatically influence sustainable development of spiral bevel gear product. Sufficient guidance, in this respect, is lacking in the scholarly or practitioner literature. In this work, focusing on spiral bevel gear production, we further examine dry-cutting technology in terms of application and sustainability implications. We introduce bending fatigue life design into gear dry-grinding by considering various economic, environmental and social attributes. We also develop bending fatigue life oriented tooth flank dry-grinding tool modification by incorporating a high life cycle assessment (LCA) and low life cycle cost (LCC). At first, data-driven tool modification design relating to dry-grinding tool parameters is developed. Then, finite element method (FEM) based root bending fatigue assessment is performed by using the multiaxial fatigue damage model. Here, with data-driven finite element modeling, simulated loaded tooth contact analysis (SLTCA) is employed to root bending stress determination. They were introduced into the multiaxial fatigue damage model based fatigue life assessment. Moreover, focusing on the minimum fatigue at dangerous point namely fatigue limit, bending fatigue life oriented dry-grinding tool modification model considering geometric accuracy is established. Then, data-driven adaptive feedback and optimization is performed by using tool modification. The final output tool modification parameters can be used to obtain the cleaner manufacturing of gear product both flank geometric accuracy and fatigue life. Finally, the numerical instance was given to verify the proposed method. By building a bridge between the tool parameters in early design and the fatigue life in actual transmission, the proposed method can get a significantly important access to cleaner manufacturing of spiral bevel gears product. [ABSTRACT FROM AUTHOR]

[Display omitted] • Carbon-wrapped SnO 2 QDs are anchored on g-C 3 N 4 (SnO 2 @C/CN) with morphology control. • Carbon encapsulation facilitates the electron transfer from g-C 3 N 4 to SnO 2 QD. • Internal electric field promotes the separation and migration of photogenerated charges. • SnO 2 @C/CN achieves the HER rate of 2544.3 μmol h−1 g−1 with 9.63 % AQE (λ = 420 nm). Graphitic carbon nitride (g-C 3 N 4) is a promising material for photocatalytic water splitting but suffers from the self-agglomeration and fast recombination of photogenerated electron–hole pairs. Tin oxide (SnO 2) has a high electron extraction ability and can play a key role in the charge separation and transfer dynamics of composites. Herein, we report a 0D/2D heterostructure of carbon-encapsulated SnO 2 quantum dots (SnO 2 @C QDs) anchored on g-C 3 N 4 nanosheets (SnO 2 @C/CN). The construction of interface between SnO 2 @C and g-C 3 N 4 dramatically increases the surface area and the number of active sites for photocatalytic hydrogen evolution reaction (HER) and provides a driving force for efficient charge separation/transfer kinetics. The carbon layer encapsulating SnO 2 QDs acts as a bridge that facilitates electron transfer from g-C 3 N 4 to SnO 2 QDs. The champion SnO 2 @C/CN achieves an exceptional HER rate of 2,544.3 μmol g−1 h−1 (with 3 wt% Pt) with an apparent quantum efficiency of 9.63 % (λ = 420 nm) and excellent photostability. A photoactivity enhancement mechanism is proposed based on the interfacial energy band alignment. This work provides insights into the designing of heterostructured photocatalysts of enhanced charge separation via interface engineering. [ABSTRACT FROM AUTHOR]

ZSM-5 supported cobalt tungstate catalyst (CoWO 4 /ZSM-5-DR) was prepared by a facile dissolution-regrowth strategy. The sulfur removal could reach 100% within 5h over the obtained CoWO 4 /ZSM-5-DR. [Display omitted] • CoWO 4 /ZSM-5-DR was prepared via a facile dissolution-regrowth strategy. • The surface structure was reconstructed including the morphology and the pore size. • Removal of DBT could reach 100 % by CoWO 4 /ZSM-5-DR within 5 h. • CoWO 4 /ZSM-5-DR showed superior cycling stability even after 6 cycles. • O 2 •− was deduced as the main active species for the conversion of DBT to DBTO 2. Compared with homogeneous catalysts, heterogeneous catalysts have greater separability and recyclable properties. Yet, the uneven distribution of active sites in the conventional synthetic method is a challenge. Herein, ZSM-5 supported cobalt tungstate catalyst (CoWO 4 /ZSM-5-DR) was prepared by a facile dissolution-regrowth strategy under mild conditions. In comparison to the supported CoWO 4 catalyst generated by impregnation, the catalyst demonstrated a higher desulfurization efficiency in oxidative desulfurization due to the surface structural reconstruction of ZSM-5 and the uniform dispersion of the active substances. The as-prepared CoWO 4 /ZSM-5-DR catalyst can achieve 100 % sulfur removal within 5 h, which exhibits good stability and a high removal rate even after 6 cycles. This work provides new insight into supported binary metal oxide catalysts with highly homogenous dispersion and effectivity. [ABSTRACT FROM AUTHOR]

[Display omitted] • Graphdiyne-like boron nitride nanosheets were transformed into SAAs. • SAAs exhibit an enhanced adsorption capacity. • The CO 2 adsorption mechanism was evaluated in detail. • Charge transfer is the main factor in CO 2 adsorption. Developing an efficient adsorbent with optimal absorption capacity for carbon dioxide (CO 2) has always been a significant issue. Recently, single-atom adsorbents (SAAs) have been highlighted with special interest as a promising material with a wide range of applications. Nevertheless, comprehending the intricate mechanisms of gas adsorption on SAAs remains an enormous challenge. Herein, we have systematically evaluated the adsorption mechanisms over the transition metals (Fe, Co, Ni, Cu, and Zn) embedded onto the graphdiyne-like boron nitride monolayer using density functional theory calculations. Results show that SAAs exhibit a promoted capacity compared to the pristine graphdiyne-like boron nitride monolayer, mainly ascribed to the electron donation and back-donation mechanism between metal and CO 2. Further, BNene/Fe is favorable for CO 2 adsorption with the strongest interaction energy (−20.7 kcal mol−1). We hope this work will facilitate the design of SAAs in the field of gas adsorption. [ABSTRACT FROM AUTHOR]

The multi-step reaction of CO2 over basic catalysts significantly improves the diversity of products, vividly embodying the ability of green chemistry to turn waste into treasure. However, under a Lewis acidic CO2 atmosphere, the activity maintenance of the multi-step reaction puts forward higher requirements for the reversible regeneration ability of the basic catalysts. Novel Lewis–Brønsted binary basic poly(ionic liquid)s (LB-PILs) were successfully developed through a radical copolymerization followed by ion-exchange strategy, and were applied to the two-step synthesis of dimethyl carbonate (DMC) by coupling CO2 cycloaddition and CH3OH transesterification without any cocatalyst. Relying on the activation of CO2 by Lewis basic tertiary N and the thermal recovery of nucleophilic HCO3− to stronger Brønsted basic OH− with the help of temperature control in CH3OH transesterification, the LB-PILs presented high activity, stable repeatability and linear carbonate universality. In situ IR analysis and Knoevenagel condensation, combined with theoretical calculations, provided reliable support for the ingenious incorporation of reversible regeneration of basic catalysts in a Lewis acidic CO2 atmosphere and multi-step coupling reaction process of CO2. [ABSTRACT FROM AUTHOR]

Abstract: The magnetic and electronic properties of Ba2MnMoO6 are investigated by using the full-potential linearized augmented plane-wave method, with both generalized gradient approximations (GGA) and GGA+ U approaches. The calculated results indicate that parameter U plays a vital role in the electronic structure characterization. The ground state is found to be antiferromagnetic and insulating. In terms of the Heisenberg model, the nearest-neighbor and the next-nearest-neighbor magnetic interaction parameters are determined to be J 1 =−1.17meV and J 2 =−0.87meV. The valence states of Mn and Mo are suggested to be divalent and hexavalent respectively, in agreement with the experimental data. [Copyright &y& Elsevier]

• A novel electronic modulation strategy on metal-free catalyst via organic modification was proposed. • The electron transfer effect was well proved and the electron transfer direction was clarified. • A deep oxidative desulfurization can be achieved with the residual sulfur content less than 10 ppm. • The mechanism of the improved catalytic activity was illustrated clearly. Tuning electronic structure of metal catalysts by organic modification is an efficient strategy for domination of their catalytic performances. However, the electronic structure tuning over metal-free catalysts remains to be a challenge. In this work, an organic modification strategy with deep eutectic solvents (DES) as organic modifier over metal-free catalysts was proposed to tune the electronic structure of hexagonal boron nitride (h-BN). Detailed experiments showed that the electronic properties of h-BN was rationally tuned by the introduced DES, in which the B atoms in h-BN were positively charged. Meanwhile, the modulated electronic properties can lower the activation energy for the generation of hydroxyl radicals (•OH) from hydrogen peroxide (H 2 O 2), thus leading to a promoted catalytic performance in oxidative desulfurization. This finding may pave a new strategy for tuning metal-free catalysts with highly-active catalytic performance. An organic ligand modification strategy over metal-free boron nitride catalyst. [Display omitted] [ABSTRACT FROM AUTHOR]

Abstract: Dok adapter proteins have been primarily implicated in negative regulation of tyrosine kinase signaling, but Dok-4 has been reported to exert both inhibitory and stimulatory effects. We have identified a splice variant of Dok-4, Dok-4b, which contains a 39 aa insert within the its C-terminal region. The ∼45kDa Dok-4b protein was detected in several human epithelial cell lines. Based on genomic sequences, Dok-4b was also predicted to exist in primates and possibly bovines, but not in rodents or other species. Compared to Dok-4, Dok-4b inhibited the tyrosine kinase-induced activation of both Erk and Elk-1 more strongly. Truncation of the C-terminal region of Dok-4 (Dok-4 ΔCT) also enhanced the inhibitory activity of Dok-4, whereas expression of the isolated C-terminal domain enhanced Elk-1 activation, suggesting that the N-terminus and C-terminus of Dok-4 possess opposing inhibitory and stimulatory properties, respectively, the balance of which is altered by alternative splicing of Dok-4 to Dok-b. [Copyright &y& Elsevier]

Iron, copper oxides composite particles (Fe/Cu oxides CPs) were produced using rapid, single-step, green and sustainable pathway from biomolecules of pine needle extract and were adopted as a potential adsorbent for the removal of norfloxacin (NOR) and ofloxacin (OFLX) from aqueous solution. To understand the morphologies and properties of Fe/Cu oxides CPs, surface analysis via SEM image, EDS, TEM, XPS, BET and FTIR pattern were employed. The effects of factors such as contact time, reaction temperature, initial pH, initial concentration and ionic strength on the adsorption capacity of NOR or OFLX onto Fe/Cu oxides CPs were studied. Kinetic analysis confirmed that the kinetic data were well described by Double-constant rate equation. The experimental equilibrium data were well fitted by Redlich-Peterson, Koble-Corrigan and Dubinin-Radushkevich models and the maximum adsorption capacity of Fe/Cu oxides CPs calculated by Langmuir model for NOR and OFLX was 1.64 mmol/g and 1.26 mmol/g at 293 K, respectively. Thermodynamic parameters such as Gibbs free energy (ΔG), enthalpy (ΔH) and entropy (ΔS) were calculated and the results indicated that the NOR or OFLX adsorption onto Fe/Cu oxides CPs was spontaneous and endothermic. Adsorption mechanism of NOR and OFLX may be involved a combination of electrostatic interaction, the formation of hydrogen bonds, π-π stacking interactions, surface complexation, hydrophobic interaction. [ABSTRACT FROM AUTHOR]

Electrochemical reduction of CO2 is a very promising route to realize carbon cycle and alleviate energy shortage. Herein, the porous zinc oxide nanosheets with hydroxyl groups on carbon paper substrates (ZnO(OH)/CP‐x,×represents the deposition time) were proved to be excellent catalysts for CO2 electroreduction to CO. As far as we know, the hydroxyl groups were first introduced into ZnO catalysts for this reaction, which can enhance the surface areas and improve the capacity of binding CO2 by the formation of hydrogen bond. Especially, the total current density could reach 44.3 mA cm−2 with 97.8 % Faradaic efficiency (FE) of CO over ZnO(OH)/CP‐600 catalysts with moderate hydroxyl groups in 1‐butyl‐3‐methylimidazolium hexafluorophosphate ([Bmim]PF6, 30 wt%)/acetonitrile/H2O (5 wt%) ternary electrolytes at −2.0 V versus Ag/Ag+, although the self‐reduction of the catalysts could be occurred simultaneously during electrolysis. Besides, the composition of the electrolytes also can significantly modulate the catalytic activity and selectivity of CO. The outstanding performance of ZnO(OH)/CP‐600 catalyst resulted mainly from the introduction of hydroxyl groups, high surface area, good contact with the substrate, and synergy effect between the catalyst and the electrolyte. [ABSTRACT FROM AUTHOR]

With the rapid development of lithium-ion batteries (LIBs), the selective recovery of lithium and other valuable metals from spent LIBs is in urgent need because of the shortage of Li and valuable metals along with the toxicity of components. Herein, a tandem leaching system for the selective recovery of Li and other valuable metals (Co, Mn) from spent LIBs was engineered by employing formic acid and its derived deep eutectic solvent (DES) as leaching agents. Results illustrate that Li can be selectively leached by formic acid, and other valuable metals can be recycled by DES. The selective leaching of valuable metals from different types of LIBs were investigated, and it was found that the tandem leaching system was applicable to the different types of LIBs with recovery efficiencies >99% for valuable metals at leaching temperatures as low as 70 °C. This finding may provide an environmentally friendly and effective approach for the selective recovery of Li and other valuable metals from spent LIBs. [ABSTRACT FROM AUTHOR]

Designing atomically defective adsorbents with high specific surface area has emerged as a promising approach to improve sorption properties. Herein, hierarchical porous boron nitride nanosheets with boron vacancies (Bv-BNNSs) were in-situ synthesized via a one-step ZnCl 2 -assisted strategy. Being benefitted from the dual-functional template of zinc salt, highly-active boron vacancies and abundant hierarchical pores were simultaneously generated in the Bv-BNNSs framework. By employing the boron vacancies engineering strategy, the morphological and electronic structures were controllably tuned. Meanwhile, the specific surface area was improved to as high as 1104 m2/g. Owning to the abundance of accessible surface active-sites, the sorption capacity to antibiotic tetracycline (TC) on Bv-BNNSs was boosted by 38% compared to the pristine boron nitride nanosheets (BNNSs). Detailed fitting results showed that TC sorption on Bv-BNNSs obeyed the pseudo-second order kinetic equation and the Freundlich isotherm model. The pi − pi interaction with a multi-layered stacking form was proposed as the dominated sorption mechanism. Furthermore, DFT calculations verified that the interaction energy between Bv-BNNSs and TC was enhanced. The high activity, excellent selectivity, and remarkable durability of the Bv-BNNSs nanomaterial suggest the great potential in practical wastewater treatment. [ABSTRACT FROM AUTHOR]

The defective MoO 3 derived from Mo-based MOF was highly dispersed on nitrogen-doped porous carbon (V O -MoO 3 @NPC) by a single-step carbonization treatment. Notably, V O -MoO 3 @NPC realizes an extraordinary desulfurization efficiency of 99.1% within 20 min coupled with an exceedingly remarkable TOF of 96.2 h−1 owing to plentiful oxygen vacancies and effective electron transfer. [Display omitted] • V O -MoO 3 @NPC derived from Mo-MOF was prepared via an in situ annealing strategy. • Richer oxygen vacancies are formed due to the stronger metal-support interaction. • Incorporating nitrogen facilitates the electron transfer by shrinking the band gap. • V O -MoO 3 @NPC realizes an outstanding catalytic ODS activity of 99.1% within 20 min. • TOF can reach 96.2 h−1 by V O -MoO 3 @NPC but only 50.2 h−1 by V O -MoO 3 @PC. Electron transfer between supports and metal oxides is of great significance in optimizing the catalytic activity, while this is still an open issue for understanding its real role in the oxidative desulfurization (ODS) process. Herein, the defective molybdenum trioxide derived from molybdenum-based metal–organic frameworks was highly dispersed on nitrogen-doped porous carbon (V O -MoO 3 @NPC) by a single-step carbonization treatment. The uniform integration of organic moieties and the unique porous structure of carbonaceous materials are conductive to the active site exposure and mass transfer process during the ODS reaction. Meanwhile, richer oxygen vacancies are generated due to the weakened Mo-O bonds, which is pertinent to the promoted electron transfer between nitrogen-doped porous carbon and molybdenum trioxide by shrinking the band gap. The results manifest that the obtained V O -MoO 3 @NPC realizes an extraordinary desulfurization efficiency of 99.1% within 20 min, as well as a stable recyclability of up to 9 times. Furthermore, the catalyst delivers an extremely remarkable turnover frequency of 96.2 h−1, which is far superior to that of previously reported molybdenum-based catalysts. This manuscript provides new inspiration for designing excellent ODS catalysts by introducing electron-rich nitrogen to construct strong metal-support interactions. [ABSTRACT FROM AUTHOR]

[Display omitted] • BN-UM6:4 exhibits an excellent ADS capacity of 47.2 mg S/g adsorbent. • The porosity was finer adjusted by modifying the composition of N precursor. • Compared to solvent-based method, solvent-free method achieves higher micropore ratio. • Abundant micropores effectively enhance ADS performance (R2 > 0.8). • S-N covalent bonds and C-H···N hydrogen bonds are the main driving. Construction of structurally stable and highly porous materials, like hexagonal boron nitride (h-BN), is a prerequisite for achieving efficient adsorptive desulfurization (ADS). Nevertheless, the present constraints in precisely adjusting the pore structure parameters of BN impede its further utilization in the field of adsorption. In this study, highly porous boron carbon oxynitride (BCNO) adsorbents were synthesized via a straightforward, one-step solvent-free reaction. By modifying the composition of nitrogen (N) precursors, it was possible to finer tuning the micropore ratio thereby leading to a substantial increase in micropore surface area. Moreover, the fitting coefficients (R2) between S micropore , V micropore , and adsorption capacity are 0.81959 and 0.80547, indicating a strong correlation between the microporous structure and the ADS performance. The prepared BCNO-UM6:4 adsorbent showed excellent adsorption performance with a capacity of 47.2 mg S/g adsorbent, surpassing the adsorbents synthesized using solvent-based methods (39.4 mg S/g adsorbent) and single-source N synthesis (BCNO-U18 32.1 mg S/g adsorbent, BCNO-M6 12.1 mg S/g adsorbent). Experimental results revealed that the main adsorption mechanism is multi-layer adsorption by the micropore filling. Density functional theory (DFT) revealed that the newly formed S-N covalent bonds and C-H···N hydrogen bonds are the main driving forces. In summary, this synthetic method expands the production pathway of porous BCNO and has potential application in various research fields. [ABSTRACT FROM AUTHOR]

Mo-based MOFs with various organic linkers showed fast desulfurization performance and high stability. [Mo(O 2)] was deduced as the main active oxygen species for the conversion of DBT to DBTO 2. The sulfur removal could reach 99.4% within 12 min over the obtained Mo-MOF-PI due to the high dispersion of Mo atoms. [Display omitted] • Mo-MOFs were constructed through assembling various organic linkers and MoO 3. • Mo-MOF-PI could achieve 99.4% sulfur removal with only 12 min. • ODS can be enhanced by the stronger interaction caused by the longer carbon chain. • Mo-MOF-PI showed high TOF value (19.2 h−1) and reused at least 20 times. • [Mo(O 2)] was deduced as the main active oxygen species for conversion DBT to DBTO 2. Heterogeneous catalysts are usually constructed by immobilizing active species on appropriate supports. However, the dispersibility is difficult to precisely control. In this work, three representative Mo-based MOFs (Mo-MOFs) were constructed by assembling various organic linkers and MoO 3 , where the Mo atoms are homogeneously dispersed due to the coordination. The results illustrated that the obtained Mo-MOF-PI synthesized with 2-propyl imidazole as the ligands exhibited an extremely fast reaction rate, achieving 99.4% sulfur removal of DBT within only 12 min. Compared to other similar catalysts, Mo-MOF-PI showed much higher catalytic activity with a turnover frequency value of 19.2 h−1. Moreover, it can be reused at least 20 times without a dramatic reduction in catalytic performance. Thus, the as-prepared Mo-MOF catalysts show great potential in large-scale industrial applications. [ABSTRACT FROM AUTHOR]

Novel 3D porous Cd(II) ion-imprinted polymer (Cd(II)-IIP) microspheres based on octavinyl polyhedral oligomeric silsesquioxane (OV-POSS) were prepared by reversible addition-fragmentation chain transfer (RAFT) polymerization technique combined with the synergistic effect of N-hydroxymethylacrylamide (NMA) and 1-vinylimidazole (1-VI) as bifunctional monomers. RAFT polymerization could achieve a controllable synthesis of polymer networks on OV-POSS. The structure, composition and properties of Cd(II)-IIP were systematically investigated by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, atomic force microscope, water contact angle and thermogravimetric analysis. The results showed that the adsorbent, with a water contact angle of 0 ° and superhydrophilicity, has a high potential for application in aqueous phase systems. Different parameters influencing the sorption performance of Cd(II)-IIP, such as OV-POSS ratio, functional monomers ratio, adsorbent dosage, pH and adsorption time were optimized. Under optimal conditions, the maximum adsorption amount of Cd(II)-IIP for Cd(II) was 80.21 mg/g, and the adsorption equilibrium state could be reached within 40 min. The sorption kinetics proved that the sorption was chemisorption and the rate-limiting step was intraparticle diffusion. Thermodynamic studies showed that Cd(II) sorption was a spontaneous endothermic process. Importantly, XPS analysis, density functional theory (DFT) and frontier molecular orbital (FMO) theory calculations showed that the sorption of Cd(II)-IIP was attributed to the coordination of O and N atoms with Cd(II) on NMA and1-VI, respectively. Actual water sample analysis results indicated that Cd(II)-IIP was an adsorbent of great application potential. [Display omitted] • Controllable synthesis of 3D porous Cd(II)-IIP using RAFT polymerization in concert with bifunctional monomers. • Cd(II)-IIP exhibited superior hydrophilicity and excellent selectivity compared to matrix material OV-POSS. • A combination of experiments and DFT calculations elucidated the adsorption mechanism. [ABSTRACT FROM AUTHOR]

Novel 3D porous Cd(II) ion-imprinted polymer (Cd(II)-IIP) microspheres based on octavinyl polyhedral oligomeric silsesquioxane (OV-POSS) were prepared by reversible addition-fragmentation chain transfer (RAFT) polymerization technique combined with the synergistic effect of N-hydroxymethylacrylamide (NMA) and 1-vinylimidazole (1-VI) as bifunctional monomers. RAFT polymerization could achieve a controllable synthesis of polymer networks on OV-POSS. The structure, composition and properties of Cd(II)-IIP were systematically investigated by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, atomic force microscope, water contact angle and thermogravimetric analysis. The results showed that the adsorbent, with a water contact angle of 0 ° and superhydrophilicity, has a high potential for application in aqueous phase systems. Different parameters influencing the sorption performance of Cd(II)-IIP, such as OV-POSS ratio, functional monomers ratio, adsorbent dosage, pH and adsorption time were optimized. Under optimal conditions, the maximum adsorption amount of Cd(II)-IIP for Cd(II) was 80.21 mg/g, and the adsorption equilibrium state could be reached within 40 min. The sorption kinetics proved that the sorption was chemisorption and the rate-limiting step was intraparticle diffusion. Thermodynamic studies showed that Cd(II) sorption was a spontaneous endothermic process. Importantly, XPS analysis, density functional theory (DFT) and frontier molecular orbital (FMO) theory calculations showed that the sorption of Cd(II)-IIP was attributed to the coordination of O and N atoms with Cd(II) on NMA and1-VI, respectively. Actual water sample analysis results indicated that Cd(II)-IIP was an adsorbent of great application potential. [Display omitted] • Controllable synthesis of 3D porous Cd(II)-IIP using RAFT polymerization in concert with bifunctional monomers. • Cd(II)-IIP exhibited superior hydrophilicity and excellent selectivity compared to matrix material OV-POSS. • A combination of experiments and DFT calculations elucidated the adsorption mechanism. [ABSTRACT FROM AUTHOR]

Antibiotic resistance (AR) has become a potential concern to public health. It is mainly associated with the overuse and misuse of antibiotics in the environment. Several factors influence the development and dissemination of antibiotic resistance genes (ARGs); however, the relative contribution of these factors has been scarcely characterized. To study the impact of each factor, we examined the effects of five antibiotics, eight heavy metals, five physicochemical properties, and bacterial community on the abundance of 310 ARGs in agricultural soils collected near a smelter. Tetracycline was found in the highest levels of all the samples compared to the other four antibiotics, with the most severe contamination (1738.534 μg/kg) occurring in the sample farthest from the plant (2556 m), whereas the highest copy number of ARGs (sulfonamide resistance genes, 3.63 × 10−1 copies/16SrRNA) and the worst heavy metal pollution (Cd, 18.900 mg/kg; Pb, 1938.000 mg/kg) were detected in the sample closet to the plant (741 m). Pearson and Spearman rank correlation analysis showed that the abundance of 84 ARGs was impacted by these four factors in the soil. The bacterial phyla contributed to 79.76% of ARGs variation, whereas antibiotics, heavy metals, and physicochemical properties contributed 4.76%, 1.19%, and 3.57%, respectively. Bacterial community was the main factor influencing the distribution of ARGs. Antibiotics and heavy metals may affect the distribution of ARGs not only by themselves but also by influencing the structure of bacterial community in the soil. The research provides insights into the different contributions of factors to AR control. Image 1 • The profiles of ARGs and bacterial communities in soil nearby a smelting plant were characterized. • Bacterial community was the main factor affecting the distribution of ARGs in this soil. • Antibiotics and heavy metals may impact ARGs distribution by affecting soil bacterial structure. [ABSTRACT FROM AUTHOR]

The physical properties of the double perovskite A 2 BB'O 6 are closely related to the B-site cationic arrangement, which directly affects the crystal morphology, magnetic coupling and electronic structure. Herein, the impact of B-site antisite defects on the magnetic and electronic properties of double perovskite Pb 2 FeOsO 6 has been investigated using spin-polarized first-principles calculations. Our calculations demonstrate that B-site ordered Pb 2 FeOsO 6 is a ferrimagnetic semiconductor with the saturated magnetic moment of ~2.27 μ B f.u.−1, mainly generated from B-site Fe and B′-site Os antiferromagnetic coupling. With the introduction of B-site antisite defects, the crystal lattices nearly maintain the original structure of the ordered Pb 2 FeOsO 6 , although the internal atomic arrangements are reconstructed. Nevertheless, the saturated magnetic moment is sharply reduced in Fe/Os disordered configurations, which originates from the additional Os–Os and Fe–Fe antiferromagnetic coupling, and consequently induces Os–Os, Os–Fe and Fe–Fe spins interaction competition. Further electronic structure analyses indicate that the B-site antisite defects do not alter the semiconducting performance of Pb 2 FeOsO 6. Our study sharpens the understanding of the effects of cationic ordering on the physical properties of double perovskites and provides an alternative avenue for tailoring their characteristics. This work illustrates the nonnegligible effect of B-site atomic disorder on the atomic distribution, spin interaction arrangements and electronic transport properties in double perovskite Pb 2 FeOsO 6. Image 1 [ABSTRACT FROM AUTHOR]

The atmospheric turbulence can severely affect the azimuth imaging of the Synthetic Aperture Ladar (SAL). Based on a neural network, this study generates atmospheric phase screens complied with marine atmosphere spectrum. The SAL imaging results with different turbulence intensities and laser wavelengths are calculated, and the changing law of the ratio of real aperture length to atmospheric coherence diameter with turbulence intensity under different slant ranges and laser wavelengths are analyzed in this paper. The results suggest that the SAL imaging becomes worse as the turbulence intensity is stronger, and even the target is not able to be distinguished. A longer laser wavelength can be used to alleviate the defocus effect, and the phase error compensation algorithm based on marine phase screens can effectively improve the SAL imaging quality to guarantee the real–time process of echo signals of SAL in the marine atmosphere. [ABSTRACT FROM AUTHOR]

• Dual Brønsted DESs were designed as extractants and catalysts for oxidative desulfurization. • The reaction mechanism was studied in depth through experimental and theoretical method. • Synergistic effect made the DES showed higher catalytic activity than other DESs. • Decreasing viscosity of DES was verified as effective strategy to improve reaction rate. Deep eutectic solvents (DESs) are generally used as attractive solvents or extractants rather than catalysts in the field of synthesis and separation. Herein, dual Brønsted acidic DESs were prepared by mixing sulfonated quaternary ammonium and oxalic acid as extractants and catalysts for deep oxidative desulfurization. Compared to the DESs with single acidic group, the dual acidic DESs exhibited much higher catalytic activity likely due to the synergistic effect. The 1H NMR study indicated that the weak interaction between DES and sulfur compounds led to a low extraction capacity. However, the sulfur removal could reach 97.7% under optimized reaction conditions. Density functional theory (DFT) calculations demonstrated that sulfonic group and carboxylic group are of equal importance to desulfurization performance. Further, the desulfurization efficiency was also strongly affected by the viscosity of DESs. Here, we put forward a new strategy that the reaction time could be sharply shortened to 40 min and 100 min by adding low viscous acetonitrile and polyethylene glycol into DES to form mixing reaction system, respectively. [ABSTRACT FROM AUTHOR]

Sulfur compounds in oil phase were captured into the catalyst phase, then oxidized to their corresponding sulfones in the presence of molecular oxygen. • A series of electrophilicity-tunable ionic liquids were successfully synthesized via a facile ion exchange method. • Both cation and anion parts in ionic liquid played an important role in ODS process. • The prepared ionic liquid [C 4 VIM]PMoV 2 exhibited high efficiency in aerobic ODS process under mild conditions. • The structure-function relationship was investigated in detail from various methods. With increasing stringent standard of sulfur content in fuels, deep desulfurization with high-efficiency is necessary for ecological and environmental demands. Herein, vanadium-substituted polyoxometalate-based ionic liquids with tunable electrophilicity were facilely synthesized through ion exchange method, and applied in the aerobic oxidative desulfurization. The experimental results indicated that both imidazole cation and polyoxometalate anion played a vital role in the desulfurization process. The prepared materials have a good performance on the degradation of aromatic sulfur compounds, which can reach up to 98.9 % under optimal conditions. Moreover, the structure-function relationship was also investigated in detail, as well as the proposed mechanism. [ABSTRACT FROM AUTHOR]

Background: Penicillin allergy is frequently reported in adults and children. Recent studies suggest that microbiota plays a key role in the development and progression of allergy. In this study, the relationship between vaginal microbiome and pregnant women with penicillin allergy was investigated. Methods: Vaginal samples before labor from 12 pregnant women with penicillin allergy and 15 non-allergic pregnant women were collected. Bacterial community structure of all study subjects and the discrepancies between the two groups were analyzed using 16S rRNA sequencing based on Illumina Hiseq 2500 platform. Results: The abundant phyla among all participants were Firmicutes, Actinobacteria and Bacteroidetes. The predominant genus was Lactobacillus. Compared to non-allergic pregnant women, Actinobacteria, Coriobacteriaceae, Lachnospiraceae, Paraprevotella and Anoxybacillus significantly decreased, whereas Deltaproteobacteria, Peptostreptococcaceae, Enterococcus and Megamonas were more abundant in penicillin allergic women. Additionally, obvious discrepancies were observed in the co-abundance network at the genus level between the two groups. Conclusions: There were differences in the microbial community structure and composition of reproduction tract between penicillin allergic and non-allergic pregnant women. These shifts may be related to maternal and neonatal health. [ABSTRACT FROM AUTHOR]

Within RCu3Mn4O12 (R=Rare earth), besides the expected ferrimagnetic order of Mn and Cu ions below TC1, R magnetic moments also play an important role at lower temperatures TC2, leading to their peculiar magnetic behavior. By first-principles calculation, we found that along the series from La to Lu, TC1 monotonically increased due to the ionic radius (IR) induced chemical pressure, as experimentally observed, while TC2 is closely related to the atomic radius of R. Additionally, the magnetic anisotropy energy (ΔEani) along the series is found to be correlated with the total magnetic moment of R ion. [ABSTRACT FROM AUTHOR]

The interaction energy (Δ E int) between adsorbent and TC was increased from −37.0 to −60.2 kcal/mol when N-defects was engineered in BNNSs. The adsorption capacity of N-defective BNNSs for TC was increased to ~1100 mg/g. • N-defective boron nitride nanosheets were in situ synthesized via alkali-assisted strategy. • The tuned electronic structure and enlarged pore size simultaneously facilitate the TC sorption capacity to ~1101 mg/g. • DFT calculations confirmed the enhanced adsorptive strength between N-defective BNNSs and TC. • Multilayer π-π stacking interactions were the dominated mechanism for the sorption. • Defect-tuning strategy was a promising feasible approach to engineer high-efficacy adsorbents. Engineering structure defects in boron nitride for enhancing adsorption performance is imperative for the rational design of a high-efficient adsorbent. Herein, boron nitride nanosheets (BNNSs) with nitrogen defects were in situ synthesized via a one-step alkali-assisted strategy. N-defects in BNNSs framework tune the morphological and electronic structure of the nanomaterial, strengthening the interaction between sorbents and pollutants, and resulting in the promotion of antibiotics removal. The enhanced adsorptive strength between N vacancy defect and tetracycline (TC) were further confirmed by density functional theory (DFT) calculations. The sorption of TC was well fitted to the pseudo-second order kinetics model and Freundlich isotherm equation. In addition, a multilayer adsorption mechanism on heterogeneous surfaces of defective BNNSs was proposed, indicating that the adsorption is mainly dominated by π-π stacking interaction. [ABSTRACT FROM AUTHOR]