A Novel One-Pot Conversion of Aldehydes to Trifluoromethylated Bromoallylic Alcohols

One-pot conversion of aldehydes to trifluoromethylated bromoallylic alcohols in the presence of titanium isopropoxide and triphenylphosphine is described

Recent progress of sensing and machine learning technologies for process monitoring and defects detection in wire arc additive manufacturing

Wire Arc Additive Manufacturing possesses advantages of high deposition rate and low cost compared with other metal additive manufacturing processes. However, potential defects may occur during the process, such as pores, cracks, lack of fusion, inclusions, delamination, and geometrical deviations. These defects are undesirable and have negative effects. To optimize the performance of the as-built components, and to reduce the potential defects, a feasible solution is to conduct in-process sensing and provide feedback to the control system. This article aims to give a comprehensive review of recent progress on sensing technologies, such as optical, acoustic, vision, thermal, and multiple signals-based sensing technologies, and the application of machine learning to enhance the ability to extract the needed feedback from the in-process monitoring raw data. Effective monitoring of different types of defects typically requires different sensing technologies, focus points, and attentions. Multi-sensor-based sensing systems may thus be needed to provide full-scale information. These necessities include the need for in-time data fusion and more complex data processing. This review analyzes recently explored sensing technologies for their principles and remaining challenges to provide directions for future invention, exploration, and investigation

Additional file 1 of Nomogram prediction for the prediction of clinical pregnancy in Freeze-thawed Embryo Transfer

Additional file 1: Table S1. Prediction Performance of Three Prediction Models for Estimating the clinical pregnancy in FET cycles. Fig. S1. ROC curve of each related factors for clinical pregnancy in FET cycles

Data_Sheet_1_Long-Term Nitrogen Fertilization Elevates the Activity and Abundance of Nitrifying and Denitrifying Microbial Communities in an Upland Soil: Implications for Nitrogen Loss From Intensive Agricultural Systems.PDF

The continuous use of nitrogen (N) fertilizers to increase soil fertility and crop productivity often results in unexpected environmental effects and N losses through biological processes, such as nitrification and denitrification. In this study, multidisciplinary approaches were employed to assess the effects of N fertilization in a long-term (~20 years) field experiment in which a fertilizer gradient (0, 200, 400, and 600 kg N ha−1 yr−1) was applied in a winter wheat-summer maize rotation cropping system in the North China Plain, one of the most intensive agricultural regions in China. The potential nitrification/denitrification rates, bacterial community structure, and abundances of functional microbial communities involved in key processes of the N cycle were assessed during both the summer maize (SM) and winter wheat (WW) seasons. Long-term N fertilization resulted in a decrease in soil pH and an increase in soil organic matter (OM), total N and total carbon concentrations. Potential nitrification/denitrification and the abundances of corresponding functional N cycling genes were positively correlated with the fertilization intensity. High-throughput sequencing of the 16S rRNA gene revealed that the increased fertilization intensity caused a significant decrease of bacterial diversity in SM season, while changed the microbial community composition such as increasing the Bacteroidetes abundance and decreasing Acidobacteria abundance in both SM and WW seasons. The alteration of soil properties markedly correlated with the variation in microbial structure, as soil pH and OM were the most predominant factors affecting the microbial structure in the SM and WW seasons, respectively. Furthermore, consistently with the results of functional gene quantification, functional prediction of microbial communities based on 16S rRNA sequence data also revealed that the abundances of the key nitrificaiton/denitrification groups were elevated by long-term N inputs. Taken together, our results suggested that soil microbial community shifted consistently in both SM and WW seasons toward a higher proportion of N-cycle microbes and exhibited higher N turnover activities in response to long-term elevated N fertilizer. These findings provided new insights into the molecular mechanisms responsible for N loss in intensively N fertilized agricultural ecosystems.</p

Perturbation-free measurement of in situ di-nitrogen emissions from denitrification in nitrate-rich aquatic ecosystems

Increased production of reactive nitrogen (Nr) from atmospheric di-nitrogen (N2) has greatly contributed to increased food production. However, enriching the biosphere with Nr has also caused a series of negative effects on global ecosystems, especially aquatic ecosystems. The main pathway converting Nr back into the atmospheric N2 pool is the last step in the denitrification process. Despite several attempts, there is still a need for perturbation-free methods for measuring in situ N2 fluxes from denitrification in aquatic ecosystems at the field scale. Such a method is needed to comprehensively quantify the N2 fluxes from aquatic ecosystems. Here we observed linear relationships between the δ15N-N2O signatures and the logarithmically transformed N2O/(N2+N2O) emission ratios. Through independent measurements, we verified that the perturbation-free N2 flux from denitrification in nitrate-rich aquatic ecosystems can be inferred from these linear relationships. Our method allowed the determination of field-scale in situ N2 fluxes from nitrate-rich aquatic ecosystems both with and without overlaying water. The perturbation-free in situ N2 fluxes observed by the new method were almost one order of magnitude higher than those by the sediment core method. The ability of aquatic ecosystems to remove Nr may previously have been severely underestimated

Constructing Porous Carbon Electrocatalysts from Cobalt Complex-Decorated Micelles of Mesoporous Silica for Oxygen Reduction/Evolution Reaction

The construction of a porous carbon structure with a high specific surface area is conducive to enhanced electrocatalytic activity due to the accessibility of active sites and improvement of the mass transfer. Herein, we explored the possibility of using micelles of mesoporous silica (MCM-48) as the carbon source to generate porous carbon under the confinement of MCM-48 channels. The complexes formed by Co2+ and 4,4′-bipyridine were in situ incorporated into the micelles to derive Co-related active sites (Co-Nx, Co, and Co3O4) for catalyzing the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). After pyrolysis in the N2 atmosphere and subsequent removal of the MCM-48 skeleton, the target porous carbon electrocatalyst was obtained, which exhibited promising performance for both ORR and OER and has great potential as the cathode material for Zn–air battery application. This work not only confirms the effectiveness of using the micelles of MCM-48 as the carbon source for preparing the porous carbon materials, but also provides a new platform for design and synthesis of structurally controllable materials for energy-related electrocatalytic applications

Experimental and Theoretical Studies on Ru(II)-Catalyzed Oxidative C–H/C–H Coupling of Phenols with Aromatic Amides Using Air as Oxidant: Scope, Synthetic Applications, and Mechanistic Insights

We herein illustrate the dual chelation-assisted strategy for a Ru­(II)-catalyzed oxidative ortho-C–H/C–H cross-coupling of phenols with (hetero)­aromatic amides with the aid of Zn­(OTf)2, which enables to rapidly assemble a rich library of 2′-hydroxybiphenyl-2-carboxylic acid derivatives. This protocol features broad substrate scope, excellent functional group tolerance, air as the terminal oxidant, low molar ratio of coupling partners, and scale-up synthesis. Particularly, this methodology is tolerant of more complex natural product derivatives, thus providing an opportunity for late-stage functionalization. This protocol is also used as a key step for the concise synthesis of Palomid 529, a drug in development for the treatment of glioblastoma and neovascular age-related macular degeneration. With a combination of experimental and theoretical methods, we get more insight into the essential issues of strategy determining the reaction process. The stronger coordinating ability of 2-aryloxypyridine and the less steric hindrance of amide are pivotal to the high chemoselectivity of cross-coupling over homocoupling. The first C–H bond activation step takes place at the amide substrate, and the following C–H bond activation at 2-aryloxypyridine is involved in the rate-determined step

Experimental and Theoretical Studies on Ru(II)-Catalyzed Oxidative C–H/C–H Coupling of Phenols with Aromatic Amides Using Air as Oxidant: Scope, Synthetic Applications, and Mechanistic Insights

We herein illustrate the dual chelation-assisted strategy for a Ru­(II)-catalyzed oxidative ortho-C–H/C–H cross-coupling of phenols with (hetero)­aromatic amides with the aid of Zn­(OTf)2, which enables to rapidly assemble a rich library of 2′-hydroxybiphenyl-2-carboxylic acid derivatives. This protocol features broad substrate scope, excellent functional group tolerance, air as the terminal oxidant, low molar ratio of coupling partners, and scale-up synthesis. Particularly, this methodology is tolerant of more complex natural product derivatives, thus providing an opportunity for late-stage functionalization. This protocol is also used as a key step for the concise synthesis of Palomid 529, a drug in development for the treatment of glioblastoma and neovascular age-related macular degeneration. With a combination of experimental and theoretical methods, we get more insight into the essential issues of strategy determining the reaction process. The stronger coordinating ability of 2-aryloxypyridine and the less steric hindrance of amide are pivotal to the high chemoselectivity of cross-coupling over homocoupling. The first C–H bond activation step takes place at the amide substrate, and the following C–H bond activation at 2-aryloxypyridine is involved in the rate-determined step

Experimental and Theoretical Studies on Ru(II)-Catalyzed Oxidative C–H/C–H Coupling of Phenols with Aromatic Amides Using Air as Oxidant: Scope, Synthetic Applications, and Mechanistic Insights

We herein illustrate the dual chelation-assisted strategy for a Ru­(II)-catalyzed oxidative ortho-C–H/C–H cross-coupling of phenols with (hetero)­aromatic amides with the aid of Zn­(OTf)2, which enables to rapidly assemble a rich library of 2′-hydroxybiphenyl-2-carboxylic acid derivatives. This protocol features broad substrate scope, excellent functional group tolerance, air as the terminal oxidant, low molar ratio of coupling partners, and scale-up synthesis. Particularly, this methodology is tolerant of more complex natural product derivatives, thus providing an opportunity for late-stage functionalization. This protocol is also used as a key step for the concise synthesis of Palomid 529, a drug in development for the treatment of glioblastoma and neovascular age-related macular degeneration. With a combination of experimental and theoretical methods, we get more insight into the essential issues of strategy determining the reaction process. The stronger coordinating ability of 2-aryloxypyridine and the less steric hindrance of amide are pivotal to the high chemoselectivity of cross-coupling over homocoupling. The first C–H bond activation step takes place at the amide substrate, and the following C–H bond activation at 2-aryloxypyridine is involved in the rate-determined step

Data_Sheet_1_Estrogen Regulates Glucose Metabolism in Cattle Neutrophils Through Autophagy.ZIP

Hypoglycemia resulting from a negative energy balance (NEB) in periparturient cattle is the major reason for a reduced glycogen content in polymorphonuclear neutrophils (PMNs). The lack of glycogen induces PMNs dysfunction and is responsible for the high incidence of perinatal diseases. The perinatal period is accompanied by dramatic changes in sex hormones levels of which estrogen (17β-estradiol, E2) has been shown to be closely associated with PMNs function. However, the precise regulatory mechanism of E2 on glucose metabolism in cattle PMNs has not been elucidated. Cattle PMNs were cultured in RPMI 1640 with 2.5 (LG), 5.5 (NG) and 25 (HG) mM glucose and E2 at 20 (EL), 200 (EM) and 450 (EH) pg/mL. We found that E2 maintained PMNs viability in different glucose conditions, and promoted glycogen synthesis by inhibiting PFK1, G6PDH and GSK-3β activity in LG while enhancing PFK1 and G6PDH activity and inhibiting GSK-3β activity in HG. E2 increased the ATP content in LG but decreased it in HG. This indicated that the E2-induced increase/decrease of ATP content may be independent of glycolysis and the pentose phosphate pathway (PPP). Further analysis showed that E2 promoted the activity of hexokinase (HK) and GLUT1, GLUT4 and SGLT1 expression in LG, while inhibiting GLUT1, GLUT4 and SGLT1 expression in HG. Finally, we found that E2 increased LC3, ATG5 and Beclin1 expression, inhibited p62 expression, promoting AMPK-dependent autophagy in LG, but with the opposite effect in HG. Moreover, E2 increased the Bcl-2/Bax ratio and decreased the apoptosis rate of PMNs in LG but had the opposite effect in HG. These results showed that E2 could promote AMPK-dependent autophagy and inhibit apoptosis in response to glucose-deficient environments. This study elucidated the detailed mechanism by which E2 promotes glycogen storage through enhancing glucose uptake and retarding glycolysis and the PPP in LG. Autophagy is essential for providing ATP to maintain the survival and immune potential of PMNs. These results provided significant evidence for further understanding the effects of E2 on PMNs immune potential during the hypoglycemia accompanying perinatal NEB in cattle.</p