Facile access to α-silylmethylamidines by BF3-catalyzed hydroamination of silylynamides with amines.

The metal-free BF3-catalyzed hydroamination of silylynamides with amines allows facile and efficient synthesis of α-silylmethylamidines in moderate to excellent yields (up to 99%) with a broad substrate scope and excellent functional group compatibility under mild reaction conditions. This protocol offers the first synthetic route to silyl-incorporated amidine compounds, which features the use of Lewis acid BF3 as the catalyst and easily available silylynamides as the silicon source. Considering the biological importance of amidine scaffolds and silyl groups, the easy incorporation of these two structural units should make great sense for medicinal chemistry. Notably, with this strategy, the installation of amidine scaffolds to drug-like molecules celecoxib and estrone is realized for the first time. A plausible mechanism involves the formation of vinyl-boron intermediates from BF3-activated ynamides, which after protodeboronation and tautomerization afford the desired products.

Risk level and removal performance of antibiotic resistance genes and bacterial pathogens in static composting with different temperatures.

The effect of different levels of temperature on resistance genes is not clear in mesophilic static composting (<50 °C). This study conducted livestock manure composting with different temperature gradients from 20 to 50 °C, it was found that the reduction rates of risk rank-I antibiotic resistance genes (from 3 % to 66 %), metal resistance genes (from -50 % to 76 %) and bacterial pathogens (from 72 % to 91 %) all increased significantly with increasing temperature from 20 to 50°C. The vulnerability of bacterial communities increased significantly, and the assembly process of bacterial communities changed from deterministic to stochastic with the increase of composting temperature. Higher temperature could accelerate the removal of thermolabile resistance genes hosts or pathogenic hosts carrying mobile genetic elements by directly or indirectly affecting organic acids content. Therefore, for soil safety, the temperature of the manure recycling process should be increased as much as possible.

Lung megakaryocytes engulf inhaled airborne particles to promote intrapulmonary inflammation and extrapulmonary distribution.

Many lung immune cells are known to respond to inhaled particulate matter. However, current known responses cannot explain how particles induce thrombosis in the lung and how they translocate to distant organs. Here, we demonstrate that lung megakaryocytes (MKs) in the alveolar and interstitial regions display location-determined characteristics and act as crucial responders to inhaled particles. They move rapidly to engulf particles and become activated with upregulation in inflammatory responses and thrombopoiesis. Comprehensive in vivo, in vitro and ex vivo results unraveled that MKs were involved in particle-induced lung damages and shed particle-containing platelets into blood circulation. Moreover, MK-derived platelets exhibited faster clotting, stronger adhesion than normal resting platelets, and inherited the engulfed particles from parent MKs to assist in extrapulmonary particle transportation. Our findings collectively highlight that the specific responses of MKs towards inhaled particles and their roles in facilitating the translocation of particles from the lungs to extrapulmonary organs for clearance.

Influence of blood loss on cerebral oxygen saturation in paediatric patients undergoing surgery for scoliosis correction: A retrospective observational study.

AIM: Surgery for congenital scoliosis correction in children is often associated with considerable blood loss. Decrease in regional oxygen saturation (rScO2) can reflect insufficient cerebral perfusion and predict neurological complications. This retrospective observational study explored the relationship between blood loss during this surgery and a decrease in rScO2 in children. METHODS: The following clinical data of children aged 3-14 years who underwent elective posterior scoliosis correction between March 2019 and July 2021 were collected: age, sex, height, weight, baseline rScO2, basal mean invasive arterial pressure (MAP), preoperative Cobb angle, number of surgical segments, preoperative and postoperative haemoglobin level, percentage of lowest rScO2 below the baseline value that lasted 3 min or more during the operation (decline of rScO2 from baseline, D-rScO2%), intraoperative average invasive MAP, end-tidal carbon dioxide pressure, fluid infusion rate of crystalloids and colloids, operation time, and percentage of total blood loss/patient's blood volume (TBL/PBV). RESULTS: A total of 105 children were included in the study. Massive haemorrhage (TBL/PBV ≥50%) was reported in 53.3% of patients, who had significantly higher D-rScO2 (%) (t = -5.264, P < 0.001) than those who had non-massive haemorrhage (TBL/PBV <50%). Multiple regression analysis revealed that TBL/PBV (ß = 0.04, 95% CI: 0.018-0.062, P < 0.05) was significantly associated with D-rScO2%. CONCLUSIONS: Intraoperative massive blood loss in children significantly increased D-rScO2%. Monitoring should be improved, and timely blood supplementation should be performed to ensure maintenance of the blood and oxygen supply to vital organs, improve the safety of anaesthesia, and avoid neurological complications.

Time series analysis of the interaction between ambient temperature and air pollution on hospitalizations for AECOPD in Ganzhou, China.

This study aimed to investigate the univariate and bivariate effects of ambient temperature and air pollutants on 57,251 inpatients with AECOPD (Acute Exacerbation of Chronic Obstructive Pulmonary Disease) in Ganzhou from January 1, 2016, to December 31, 2019. We categorized the daily mean temperature and air pollutant variables based on the exposure-response curve of the Distributed Lag Non-Linear Model. Poisson regression model was used for interaction and stratification analysis. The Relative Excess Risk due to Interaction (RERI) with 95% confidence intervals (95% CI) between daily mean temperature (Tmean) and air pollutants including NO2, PM2.5, and PM10 were - 0.428 (95% CI - 0.637, - 0.218), -- 0.227 (95% CI - 0.293, - 0.161), and - 0.119 (95% CI - 0.159, - 0.079). Further stratification analysis showed the relative risk (RR) (95% CI) of high NO2 (> 33 µg/m3) at low Tmean (≤ 28 °C) was 1.119 (95% CI 1.096, 1.142). Low temperatures with high PM10 in men and high PM2.5 in women were associated with a higher risk of AECOPD hospitalization. The results indicate a higher risk of hospitalization for AECOPD when there is with high concentrations of air pollution at low temperatures.

Progress and Challenges in Polystyrene Recycling and Upcycling.

Polystyrene is a staple plastic in the packaging and insulation market. Despite its good recyclability, the willingness of PS recycling remains low, largely due to the high recycling cost and limited profitability. This review examines the research progresses, gaps, and challenges in areas that affect the recycling costs, including but not limited to logistics, packaging design, and policymaking. We critically evaluate the recent developments in upcycling strategies, and we particularly focus on tandem and hydrogen-atom transfer (HAT) upcycling strategies. We conclude that future upcycling studies should focus on not only reaction chemistry and mechanisms but also economic viability of the processes. The goal of this review is to stimulate the development of innovative recycling strategies with low recycling costs and high economic output values. We hope to stimulate the economic and technological momentum of PS recycling towards a sustainable and circular economy.

Effect of Al and Mn substitutions on hydrogen activation performances of La-Ni-Al-Mn alloy.

To interpret the effect of Al and Mn substitutions on activation performances of La-Ni-Al-Mn alloy, the initial activation curve has been measured, which shows that the incubation time of activation is prolonged with the increase of Al content in alloy, while shortened duo to Mn substitution. Further, the first-principles calculations are employed. We find that (1) (100)/(010) surface of LaNi5 is the most stable and its stability can be improved by Al substitution for Ni while decreased by Mn substitution; (2) the preferential hydrogen adsorption sites are the hole and Ni (or Mn)-top sites; (3) Al and Mn substitutions can increase the hydrogen adsorption stability, but Al doping decreases the number of available sites, therefore retarding activation, while Mn doping guarantees the number of available sites, making activation easier; (4) H bonds covalently with neighbor Ni (or Mn) and ionically with La, together determining the stability of hydrogen adsorption.

Trace Y Doping Regulated Bulk/Interfacial Reactions of P2-Layered Oxides for Ultrahigh-Rate Sodium-Ion Batteries.

P2-phase layered cathodes play a pivotal role in sodium-ion batteries due to their efficient Na+ intercalation chemistry. However, limited by crystal disintegration and interfacial instability, bulk and interfacial failure plague their electrochemical performance. To address these challenges, a structural enhancement combined with surface modification is achieved through trace Y doping. Based on a synergistic combination of experimental results and density functional theory (DFT) calculations, the introduction of partial Y ions at the Na site (2d) acts as a stabilizing pillar, mitigating the electrostatic repulsions between adjacent TMO2 slabs and thereby relieving internal structural stress. Furthermore, the presence of Y effectively optimizes the Ni 3d-O 2p hybridization, resulting in enhanced electronic conductivity and a notable rapid charging ability, with a capacity of 77.3 mA h g-1 at 40 C. Concurrently, the introduction of Y also induces the formation of perovskite nano-islands, which serve to minimize side reactions and modulate interfacial diffusion. As a result, the refined P2-Na0.65 Y0.025[Ni0.33Mn0.67]O2 cathode material exhibits an exceptionally low volume variation (≈1.99%), an impressive capacity retention of 83.3% even at -40 °C after1500 cycles at 1 C.

Effect of high-fat diet on the fatty acid profiles of brain in offspring mice exposed to maternal gestational diabetes mellitus.

OBJECTIVE: Fatty acids play a critical role in the proper functioning of the brain. This study investigated the effects of a high-fat (HF) diet on brain fatty acid profiles of offspring exposed to maternal gestational diabetes mellitus (GDM). METHODS: Insulin receptor antagonist (S961) and HF diet were used to establish the GDM animal model. Brain fatty acid profiles of the offspring mice were measured by gas chromatography at weaning and adulthood. Protein expressions of the fatty acid transport pathway Wnt3/ß-catenin and the target protein major facilitator superfamily domain-containing 2a (MFSD2a) were measured in the offspring brain by Western blot. RESULTS: Maternal GDM increased the body weight of male offspring (P < 0.05). In weaning offspring, factorial analysis showed that maternal GDM increased the monounsaturated fatty acid (MUFA) percentage of the weaning offspring's brain (P < 0.05). Maternal GDM decreased offspring brain arachidonic acid (AA), but HF diet increased brain linoleic acid (LA) (P < 0.05). Maternal GDM and HF diet reduced offspring brain docosahexaenoic acid (DHA), and the male offspring had higher DHA than the female offspring (P < 0.05). In adult offspring, factorial analysis showed that HF diet increased brain MUFA in offspring, and male offspring had higher brain MUFA than female offspring (P < 0.05). The HF diet increased brain LA in the offspring. Male offspring had higher level of AA than female offspring (P < 0.05). HF diet reduced DHA in the brains of female offspring. The brain protein expression of ß-catenin and MFSD2a in both weaning and adult female offspring was lower in the HF + GDM group than in the CON group (P < 0.05). CONCLUSIONS: Maternal GDM increased the susceptibility of male offspring to HF diet-induced obesity. HF diet-induced adverse brain fatty acid profiles in both male and female offspring exposed to GDM.

Vascular Bundle for Exceptional Water Confinement, Transport, and Evaporation.

Nature, through billions of years of evolution, has constructed extremely efficient biosystems for transporting, confining, and vaporizing water. Mankind's ability to master water, however, is far from impeccable, and a sustainable supply of clean fresh water remains a global challenge. Here, we learn from Nature and prepare papyrus carbon (PC) from Egyptian papyrus paper as a sustainable solar desalination material. By taking advantage of the capillary pores from vascular bundles that are inherently built for transporting water in plants, PC achieves an evaporation rate of 4.1 kg m-2 h-1 in a passive single-stage device. Raman spectroscopy and thermal calorimetry show that the capillary pores pose a confinement effect to generate loosely hydrogen-bonded intermediate water, which substantially reduces the enthalpy of vaporization, allowing for exceptionally high energy efficiencies. The understanding is applicable to all nature-designed vascular plants and man-made separation and purification systems.

Selective Antitumor Effect and Lower Toxicity of Mitochondrion-Targeting Derivatization of Triptolide.

Triptolide has a significant antitumor activity, but its toxicity limits its clinical application. As the mitochondrion-targeting strategy showed an advantage in selective antitumor effect based on the higher mitochondrial membrane potential (MMP) in tumor cells than normal cells, the lipophilic cations triphenylphosphonium and E-4-(1H-indol-3-yl vinyl)-N-methylpyridinium iodide (F16) were selected as targeting carriers for structural modification of triptolide. The derivatives bearing F16 generally retained most antitumor activities, overcame its inhibition plateau phenomena, and enhanced its selective antitumor effect in lung cancer. The representative derivative F9 could accumulate in the mitochondria of NCI-H1975 cells, inducing apoptosis and a dose-dependent increase in intracellular reactive oxygen species and reducing MMP. Moreover, no effects were observed in normal cells BEAS-2B. In vivo studies showed that the developmental, renal, and liver toxicities of F9 to zebrafish were significantly lower than those of triptolide. This study provides a promising idea to relieve the toxicity problem of triptolide.

Activated carbon from Camellia oleifera shells for adsorption of Y(iii): experimental and DFT studies.

Yttrium is an important rare earth element and is widely used in fields such as special glass preparation, metallurgy, and materials science. However, it is difficult to recover yttrium ion waste from dilute solutions with traditional processes, resulting in a significant waste of rare earth resources. The simple, effective, and easy-to-operate adsorption method is the most promising method for recovering yttrium, which is of great significance for sustainable development of the rare earth industry. In this study, activated carbon was prepared from Camellia oleifera fruit shells (COS) using phosphoric acid activation, and efficient recovery of Y(iii) from the Camellia oleifera fruit shell activated carbon was studied. Adsorption equilibrium data showed that this activated carbon had a Y(iii) adsorption capacity of 35.41 mg g-1, indicating significant potential for recovery of yttrium ions. The adsorption of Y(iii) by the activated carbon prepared from COS was consistent with the Langmuir model, and the adsorption data were consistent with the pseudo second-order kinetic model, indicating that the adsorption process was primarily chemical adsorption. After adsorption, the surface of the activated carbon contained large amounts of N, O, and Y, indicating that Y(iii) was stably adsorbed. The mechanisms for adsorption of Y(iii) on three types of activated carbon were studied through DFT calculations. The results showed that Y(iii) interacted with the carbon atoms on the surfaces to form new chemical bonds. The yttrium ion adsorption capacities for the three different activated carbons decreased in the order C I > C II > C.

Transcriptomic analysis of the longissimus thoracis muscle in pigs has identified molecular regulatory patterns associated with meat quality.

Meat quality is a critical aspect of pig breeding. In addition to genetics, meat quality is also influenced by nutritional and environmental factors. In this study, three pig breeds, Shengxianhua, Jiaxing, and Qinglian Black (SXH, JXB and QLB), were used as experimental animals. Transcriptional analysis was performed on the longissimus thoracis (LT) muscle to investigate variations in intramuscular fat (IMF), inosine monophosphate (IMP), amino acids, and muscle fiber morphology across different breeds. Ingenuity canonical pathway analysis (IPA) identified biological processes and key driver genes related to metabolism and muscle development. Additionally, weighted gene co-expression network analysis (WGCNA) revealed gene modules associated with IMP. KEGG and GO analyses identified specific biological processes and signaling pathways related to IMP, including the Oxidative Phosphorylation pathway and rRNA Metabolic Processes. These findings provide novel insights into the molecular regulatory mechanisms underlying meat quality variations among pig breeds.

Grafting of Amine End-Functionalized Side-Chain Polybenzimidazole Acid-Base Membrane with Enhanced Phosphoric Acid Retention Ability for High-Temperature Proton Exchange Membrane Fuel Cells.

A high phosphoric acid uptake and retention capacity are crucial for the high performance and stable operation of phosphoric acid/polybenzimidazole (PA/PBI)-based high-temperature proton exchange membranes. In this work, amine end-functionalized side-chain grafted PBI (AGPBI) with different grafting degrees are synthesized to enhance both the phosphoric acid uptake and the acid retention ability of the accordingly formed membranes. The optimized acid-base membrane exhibits a PA uptake of 374.4% and an anhydrous proton conductivity of 0.067 S cm-1 at 160 °C, with the remaining proton conductivity percentages of 91.0% after a 100 h stability test. The accordingly fabricated membrane electrode assembly deliver peak power densities of 0.407 and 0.638 W cm-2 under backpressure of 0 and 200 kPa, which are significantly higher than 0.305 and 0.477 W cm-2 for the phosphoric acid-doped unmodified PBI membrane under the same conditions.

Enhancing the transformation of carbon and nitrogen organics to humus in composting: Biotic and abiotic synergy mediated by mineral material.

To investigate the conversion of carbon and nitrogen organic matter to humus mediated by mineral material additives through biotic and abiotic pathways, three chicken manure composting experiments were conducted using calcium superphosphate (CS) and fly ash (FA). Results showed that CS and FA promoted carbon and nitrogen organic degradation and improved compost maturity. The ratio of humic acid-like to fulvic acid-like substances for FA (30) was significantly higher than for control (18) and CS (13). Excitation-emission-matrix spectra and parallel factor analysis identified a higher transformation of protein-like components into humic-like components in FA. Network analysis showed that CS improved compost maturity by promoting the rapid conversion of humus precursors to humus, while FA increased the richness and diversity of the microbial community, such as Chloroflexi, the unique phylum in FA. Overall, CS and FA facilitated the humification process through abiotic and biotic pathways, and FA had better humification performance.

Recent advances in differential expression analysis for single-cell RNA-seq and spatially resolved transcriptomic studies.

Differential expression (DE) analysis is a necessary step in the analysis of single-cell RNA sequencing (scRNA-seq) and spatially resolved transcriptomics (SRT) data. Unlike traditional bulk RNA-seq, DE analysis for scRNA-seq or SRT data has unique characteristics that may contribute to the difficulty of detecting DE genes. However, the plethora of DE tools that work with various assumptions makes it difficult to choose an appropriate one. Furthermore, a comprehensive review on detecting DE genes for scRNA-seq data or SRT data from multi-condition, multi-sample experimental designs is lacking. To bridge such a gap, here, we first focus on the challenges of DE detection, then highlight potential opportunities that facilitate further progress in scRNA-seq or SRT analysis, and finally provide insights and guidance in selecting appropriate DE tools or developing new computational DE methods.

Mesoporous Polyimide Thin Films as Dendrite-Suppressing Separators for Lithium-Metal Batteries.

Lithium-metal batteries require the effective suppression of lithium dendrites to guarantee both high performance and safety. Today's separators have macropores allowing lithium dendrites to traverse, leading to internal short circuits and other catastrophic results. Herein, we report a mesoporous polyimide separator for dendrite suppression. The polyimide separator exhibits mesopores of 21 nm width and a high storage modulus of 1.80 GPa. This mesoporous polyimide separator assists in the electrodeposition to form flat-top protrusions instead of sharp dendrites, therefore, allowing the safe cycling of lithium-metal batteries. This work is expected to advance the development of dendrite-suppressing strategies and contribute to the revival of lithium-metal batteries.

Gestational Diabetes Mellitus Remodels the Fetal Brain Fatty Acid Profile Through Placenta-Brain Lipid Axis in C57BL/6J Mice.

BACKGROUND: Polyunsaturated fatty acids (PUFAs), especially docosahexaenoic acid (DHA), are critical for proper fetal brain growth and development. Gestational diabetes mellitus (GDM) could affect maternal-fetal fatty acid metabolism. OBJECTIVE: This study aimed to explore the effect of GDM and high-fat (HF) diet on the DHA transport signaling pathway in the placenta-brain axis and fatty acid concentrations in the fetal brain. METHODS: Insulin receptor antagonist (S961) and HF diet were used to establish an animal model of GDM. Eighty female C57BL/6J mice were randomly divided into control (CON), GDM, HF, and HF+GDM groups. The fatty acid profiles of the maternal liver and fetal brain were analyzed by gas chromatography. In addition, we analyzed the protein amounts of maternal liver fatty acid desaturase (FADS1/3), elongase (ELOVL2/5) and the regulatory factor sterol-regulatory element-binding protein (SREBP)-1c, and the DHA transport signaling pathway (Wnt3/ß-catenin/MFSD2a) of the placenta and fetal brain using western blotting. RESULTS: GDM promoted the decrease of maternal liver ELOVL2, ELOVL5, and SREBP-1c. Accordingly, we observed a significant decrease in the amount of maternal liver arachidonic acid (AA), DHA, and total n-3 PUFA and n-6 PUFA induced by GDM. GDM also significantly decreased the amount of DHA and n-3 PUFA in the fetal brain. GDM downregulated the Wnt3/ß-catenin/MFSD2a signaling pathway, which transfers n-3 PUFA in the placenta and fetal brain. The HF diet increased n-6 PUFA amounts in the maternal liver, correspondingly increasing linoleic acid, gamma-linolenic acid, AA, and total n-6 PUFA in the fetal brain, but decreased DHA amount in the fetal brain. However, HF diet only tended to decrease placental ß-catenin and MFSD2a amounts (P = 0.074 and P = 0.098, respectively). CONCLUSIONS: Maternal GDM could affect the fatty acid profile of the fetal brain both by downregulating the Wnt3/ß-catenin/MFSD2a pathway of the placental-fetal barrier and by affecting maternal fatty acid metabolism.

Identification of performance and cost in a new backwash method to clean the UF membrane: backwashing with low dosage of NaClO.

Ultrafiltration (UF) is widely used in wastewater reclamation treatments. Conventional backwashing is usually performed at regular time intervals (10-120 min) with permeate and without the addition of chemicals. Chemical enhanced backwashing (CEB) is usually applied after 70-90 filtration cycles with added chemicals. These cleaning methods cause membrane fouling and require costly chemicals. Instead of conventional backwashing, we propose herein a new backwashing method involving backwashing the effluent with low doses of sodium hypochlorite (NaClO) named as BELN. The performance and cost of UF backwashing were investigated with Beijing wastewater reclamation treatment. The results showed that the transmembrane pressure (TMP) increased from 33.2 to 48.2 kPa during hydraulic backwashing after 80 filtration cycles but increased from 33.3 to 39.3 kPa during backwashing with a low NaClO content of 20 mg/L. It was also noticed that the hydraulic-irreversible fouling index decreased from 5.58 × 10-3 m2/L to 3.58 × 10-3 m2/L with the new method. According to the three-dimensional fluorescence excitation-emission (3D-EEM), the response increased from 11.9 to 15.2% with BELN. Protein-like material was identified as the main component causing membrane fouling by blocking the membrane pores. The results indicated that the low dosage of NaClO effectively stripped the fouling layer. Finally, based on an economic evaluation, the capacity of the UF process was increased from 76,959 to 109,133 m3/d with the new method. The amount of NaClO consumed for Beijing wastewater reclamation treatment was similarly compared with the conventional backwashing in per year under BELN. The new method has good potential for application.

Dual reinforced composite membranes from in-situ ionic crosslinked quaternized chitosan filled quaternized polyvinylidene fluoride nanofiber for alkaline direct methanol fuel cell.

The main obstacle of high-performance cationic functionalization chitosan (CS) as anion exchange membranes (AEMs) is the trade-off between mechanical stability and ionic conductivity. Here, in-situ ionic crosslinking between the deprotonated hydroxyl group and quaternary ammonium group under alkaline conditions was ingeniously applied to improve the mechanical stability of highly quaternized CS (HQCS) with high IEC (>2 mmol g-1). Meanwhile, to further reduce the swelling and enhance the hydroxide conductivity, a mechanically robust hydroxide ion conduction network, quaternized electrospun poly(vinylidene fluoride) (QPVDF) nanofiber, was subsequently used as the filling substrate of in-situ crosslinked HQCS to prepare dual reinforced thin AEMs. The introduction of a robust QPVDF nanofiber mat can not only greatly improve the mechanical properties and limit swelling, but also create facile ion transport channels. Notably, the HQCS/QPVDF-74.0 composite membrane demonstrates perfect dimensional stability, high mechanical performance and excellent alkaline stability, as well as superior ionic conductivity of 66.2 mS cm-1 at 80 °C. The thus assembled alkaline direct methanol fuel cell displays a maximum power density of 132.30 mW cm-2 using 5 M KOH and 3 M methanol as fuels at 80 °C with satisfactory durability.