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A Pd-catalyzed enantioselective aminosilylation of alkenes via tandem Aza-Heck/silylation reaction under Pd/Sadphos catalysis is disclosed. A wide array of oxime esters and silicon reagents are tolerated, furnishing the chiral pyrrolines bearing one quaternary or two contiguous stereocenters in good yield with high enantioselectivity. Not only terminal alkenes but also tri-substituented internal alkenes successfully participate in the reaction, delivering vicinal stereocenters in complete diastereoselectivity and high enantioselectivity. DFT study is conducted to probe the reaction pathway and the origin of the enantioselectivity, which revealed that the stereoinduction arises from the weak interaction between the aromatic ring of the substrate fragment and naphthyl group in the ligand.
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High-index facet nanoparticles with structurally complex shapes, such as tetrahexahedron (THH) and hexoctahedron (HOH), represent a class of materials that are important for catalysis, and the study of them provides a fundamental understanding of the relationship between surface structures and catalytic properties. However, the high surface energies render them thermodynamically unfavorable compared to low-index facets, thereby making their syntheses challenging. Herein, we report a method to control the shape of high-index facet Cu nanoparticles (either THH with {210} facets or HOH with {421} facets) by tuning the facet surface energy with trace amounts of Te atoms. Density functional theory (DFT) calculations reveal that the density of Te atoms on Cu nanoparticles can change the relative stability of the high-index facets associated with either the THH or HOH structures. By controlling the annealing conditions and the rate of Te dealloying from CuTe nanoparticles, the surface density of Te atoms can be deliberately adjusted, which can be used to force the formation of either THH (higher surface Te density) or HOH (lower surface Te density) nanoparticles.
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Instigated by olfactory analysis of odorant molecules, the constitutions of 3,4-dihydrocoumarins prepared by PIFA-based oxidative cyclizations of 3-arylpropionic acids were revised by means of 2D NMR and X-ray analysis. Supported by computational analysis, the migratory mechanism of intermediate spirolactonic cations has been amended: 1,2-alkyl shifts instead of 1,2-carboxylic shifts were selectively obtained.
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AIMS: To systematically investigate the association between individual and combined metal exposure and periodontitis. METHODS: Data encompassing complete periodontal examinations and metal detection in blood and urine samples were procured from the National Health and Nutrition Examination Survey (NHANES) 2011-2014. Three statistical methods, namely weighted logistic regression, Bayesian kernel machine regression (BKMR), and weighted quantile sum (WQS) regression, were used to evaluate the independent and combined associations between metals and periodontitis. RESULTS: Elevated concentrations of blood cadmium (odds ratio [OR]: 1.73, 95% confidence interval [CI]: 1.15-2.61) and blood lead (OR: 1.17, 95 %CI: 1.02-1.34) exhibited a positive association with periodontitis, even after adjusting for potential confounding factors. The BKMR and WQS regression suggested that the co-exposure of metals was also positively associated with periodontitis. Moreover, estradiol and albumin were identified as potential mediators in the relationship between the WQS index of the 10 metals in blood and periodontitis explaining 25.36% and 2.02% of the relationship, respectively. Furthermore, generally consistent patterns of associations between metals and periodontitis and mediating roles of estrogen and albumin were observed after a series of sensitivity analyses. CONCLUSION: This study provides evidence of positive associations between elevated levels of cadmium, lead or metal mixture and periodontitis, which may be partially mediated by sex hormones and oxidative stress indicators.
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Cádmio , Chumbo , Inquéritos Nutricionais , Periodontite , Humanos , Periodontite/sangue , Periodontite/epidemiologia , Masculino , Feminino , Cádmio/sangue , Cádmio/urina , Chumbo/sangue , Adulto , Pessoa de Meia-Idade , Teorema de Bayes , Exposição Ambiental/efeitos adversos , Exposição Ambiental/análise , Metais/sangue , Metais/urina , Idoso , Modelos Logísticos , Estradiol/sangue , Estudos TransversaisRESUMO
Aiming to assess the effects of lard oil (LO) and fish oil (FO) on the nutritional value of mud crabs (Scylla paramamosain), non-targeted lipidomics analysis was performed on the muscle of crabs after eight weeks of feeding trail. Compared to FO, dietary LO reduced the content of phosphatidylethanolamine (PE) and phosphatidylserine (PS) with 18:0 bound at sn-1/3 site, the content of ether phospholipids containing 20:5n-3 (EPA) and 22:6n-3 (DHA) combined at sn-2 site, and increased the content of ether PE containing 18:0 and 18:1n-9. Furthermore, the deposition of 16:0, 16:1n-7, 18:2n-6, 18:3n-3, 20:4n-6, EPA and DHA at each site of PE, PS, phosphatidylcholine and/or triacylglycerols were reduced by dietary LO, while the DHA content at the sn-2 position of PE was increased. In conclusion, the nutritional value of mud crabs was reduced by dietary LO with the manifestation of variation in FA composition and positional distribution on phospholipids.
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Braquiúros , Gorduras Insaturadas na Dieta , Gorduras na Dieta , Animais , Óleos de Peixe/metabolismo , Braquiúros/metabolismo , Ácidos Graxos/metabolismo , Lipidômica , Músculos/metabolismo , NutrientesRESUMO
Recently, the asymmetric bifunctionalization of alkenes has received much attention. However, the development of enantioselective alkoxyalkenylation has posed a considerable challenge and has lagged largely behind. Herein, we report a new palladium-catalyzed enantioselective alkoxyalkenylation reaction, using a range of primary, secondary, and tertiary γ-hydroxy-alkenes with alkenyl halides. By employing newly identified Xu-Phos (Xu8 and Xu9) with a suitable side-arm adjacent to the PCy2 motif, a series of allyl-substituted tetrahydrofurans were obtained in good yields with up to 95% ee. Besides (E)-alkenyl halides, (Z)-alkenyl halide was also examined and provided the corresponding (Z)-product as a single diastereomer, supporting a stereospecific oxidative addition and reductive elimination step. Moreover, deuterium labeling and VCD experiments were employed to determine a cis-oxypalladation mechanism. DFT calculations helped us gain deeper insight into the side-arm effect on the chiral ligand. Finally, the practicability of this method is further demonstrated through a gram-scale synthesis and versatile transformations of the products.
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Understanding the microhabitat requirements of an animal is vital for ensuring the success of targeted conservation and microhabitat restoration measures. The big-headed turtle (Platysternon megacephalum) is a freshwater species that is distributed across Southeast Asia. Owing to the human threats posed by illegal pet trade and overharvesting for food and medicinal purposes, the species has undergone rapid decline. However, in Hainan, their microhabitat characteristics are still unknown, which is neither conducive to the conservation of the species nor to the establishment of the Hainan Tropical Rainforest National Park. This study examined the microhabitat characteristics of P. megacephalum using sample plot methods in the Diaoluo Mountain area of Hainan Tropical Rainforest National Park. Our results indicated that P. megacephalum prefers stream microhabitats with rocky substrates, several caves, and a high diversity of food sources. Microhabitat characteristics did not differ significantly between adults and juveniles. Our results suggest that protecting microhabitats and main food sources is important for the conservation of P. megacephalum. Our findings provide a reference for the protection of this species in Jianfeng Ridge, Yingge Ridge, and other areas in Hainan Tropical Rainforest National Park.
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Nanoparticles with high-index facets are intriguing because such facets can lend the structure useful functionality, including enhanced catalytic performance and wide-ranging optical tunability. Ligand-free solid-state syntheses of high index-facet nanoparticles, through an alloying-dealloying process with foreign volatile metals, are attractive owing to their materials generality and high yields. However, the role of foreign atoms in stabilizing the high-index facets and the dynamic nature of the transformation including the coarsening and facet regulation process are still poorly understood. Herein, the transformation of Pt salts to spherical seeds and then to tetrahexahedra, is studied in situ via gas-cell transmission electron microscopy. The dynamic behaviors of the alloying and dealloying process, which involves the coarsening of nanoparticles and consequent facet regulation stage are captured in the real time with a nanoscale spatial resolution. Based on additional direct evidence obtained using atom probe tomography and density functional theory calculations, the underlying mechanisms of the alloying-dealloying process are uncovered, which will facilitate broader explorations of high-index facet nanoparticle synthesis.
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Ligas , Nanopartículas Metálicas , Ligas/química , Sais , Nanopartículas Metálicas/química , Fenômenos Físicos , CatáliseRESUMO
Megalibraries are centimeter-scale chips containing millions of materials synthesized in parallel using scanning probe lithography. As such, they stand to accelerate how materials are discovered for applications spanning catalysis, optics, and more. However, a long-standing challenge is the availability of substrates compatible with megalibrary synthesis, which limits the structural and functional design space that can be explored. To address this challenge, thermally removable polystyrene films were developed as universal substrate coatings that decouple lithography-enabled nanoparticle synthesis from the underlying substrate chemistry, thus providing consistent lithography parameters on diverse substrates. Multi-spray inking of the scanning probe arrays with polymer solutions containing metal salts allows patterning of >56 million nanoreactors designed to vary in composition and size. These are subsequently converted to inorganic nanoparticles via reductive thermal annealing, which also removes the polystyrene to deposit the megalibrary. Megalibraries with mono-, bi-, and trimetallic materials were synthesized, and nanoparticle size was controlled between 5 and 35 nm by modulating the lithography speed. Importantly, the polystyrene coating can be used on conventional substrates like Si/SiOx, as well as substrates typically more difficult to pattern on, such as glassy carbon, diamond, TiO2, BN, W, or SiC. Finally, high-throughput materials discovery is performed in the context of photocatalytic degradation of organic pollutants using Au-Pd-Cu nanoparticle megalibraries on TiO2 substrates with 2,250,000 unique composition/size combinations. The megalibrary was screened within 1 h by developing fluorescent thin-film coatings on top of the megalibrary as proxies for catalytic turnover, revealing Au0.53Pd0.38Cu0.09-TiO2 as the most active photocatalyst composition.
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A long-term field experiment was conducted at a Chinese hickory (Carya cathayensis) plantation from 2011 to 2021, with the purpose of researching the effects of long-term sod cultivation on hickory plantation soil fungal communities and enzyme activities and providing experience for ecological management in other plantations. Sod cultivation included oilseed rape (Brassica chinensis, BR), Chinese milk vetch (Astragalus sinicus, AS), and oilseed rape+Chinese milk vetch (BA), and clear tillage (CT) served as a contrast. The soil fertility, fungal community composition and diversity, and soil enzyme activities were determined. The results showed that:â long-term sod cultivation significantly increased soil nutrient contents and availability, and pH increased variably from different sod cultivation treatments (P<0.05). â¡The soil fungal community composition was changed by long-term sod cultivation. The relative abundance of Ascomycota, which utilized the readily decomposed organic matter, was increased, whereas the relative abundance of Basidiomycota, which degraded stubborn organic matter, decreased. Long-term sod cultivation shifted the soil dominant genera, as BR and BA increased the relative abundance of somemycorrhizal fungi that could form mutually beneficial structures with dominant plant genera after sod cultivation,whereas AS increased the relative abundance of saprophytic fungi that could decompose the remains of dead plants and animals. The soil fertility factors including pH, available nitrogen, microbial biomass nitrogen, and water-soluble organic carbon were revealed to have a significant influence on the soil fungal composition (P<0.05). ⢠Moreover, long-term sod cultivation stimulated the activities of soil enzymes involved in the carbon and nitrogen cycle. Apart from BA, sod cultivation treatments decreased the activities of alkaline phosphatase, which was involved in the soil P turnover. The correlation analysis demonstrated that the correlations between activities of enzymes decomposing carbon and nitrogen and soil fertility were significant (P<0.05 or P<0.01). The activities of phosphatase were positively correlated with soil microbial biomass carbon and nitrogen. Long-term sod cultivation could improve soil nutrient content and availability, optimized soil fungal community structure, and promoted soil nutrient turnover enzyme activities.
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Carya , Micobioma , Solo/química , Microbiologia do Solo , Carbono , Nitrogênio/análiseRESUMO
Habitat selection and range are crucial factors in understanding the life history of species. We tracked 23 adult wild Reeves' turtles (Mauremys reevesii) from August 2021 to August 2022 in Qichun County, Hubei Province, China, to study their habitat selection, home range, and the characteristics of chosen habitats. Significant differences were observed in aquatic habitats, regarding shelter cover (Z = -6.032, p < 0.001), shelter height (Z = -6.783, p < 0.001), depth of water (Z = -2.009, p = 0.045), and distance from the edge (Z = -4.288, p < 0.001), between selected and random habitats. In terrestrial habitats, significant differences were observed in canopy cover (Z = -2.100, p = 0.036), herbage cover (Z = -2.347, p = 0.019), distance from the field edge (Z = -2.724, p = 0.006), dead grass cover (Z = -2.921, p = 0.003), and dead grass thickness (t = 3.735, df = 17, p = 0.002) between the selected and random habitats. The mean home range area observed for this turtle population was 14.34 ± 4.29 ha, the mean core home range was 2.91 ± 2.28 ha, and the mean line home range was 670.23 ± 119.62 m. This study provides valuable information on this endangered species, providing a foundation for the development of conservation plans.
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Hibernation protects turtles from extreme winter conditions. Reeves' turtle (Mauremys reevesii) is a medium-sized aquatic turtle that lives in freshwater habitats in lowland areas with still or slowly moving water. Currently, little is known regarding its overwintering behavior. In the current study, 20 Reeves' turtles from the wild were investigated using radiotelemetry in the field to determine the beginning and end dates of, and habitat selected for, hibernation. Hibernation began in late October 2021 and arousal began in March 2022. Reeves' turtles do not appear to be limited in their selection of suitable hibernation habitats, which included fish ponds, abandoned ponds (ponds not being used for farming), marshes, and abandoned fields (fields not being used for farming). In the aquatic hibernation habitats, only herbage cover was significantly different between the selected and random habitats (t = 2.525, df = 9, p = 0.033). In the terrestrial hibernation habitats, there were significant differences in the canopy (Z = -2.201, p = 0.028), slope gradient (Z = -2.032, p = 0.042), herbage cover (Z = -2.379, p = 0.017), and distance from the habitat edge (Z = -2.524, p = 0.012) between the selected and random habitats. This indicates that Reeves' turtles prefer to hibernate at the soft edges of flat habitats with low canopy and high herbage cover when hibernating in terrestrial habitats and prefer to hibernate at sites with high herbage cover when hibernating in aquatic habitats. To the best of our knowledge, this is the first study to investigate hibernation in wild Reeves' turtles in the field, and the results identify key ecological variables correlated with habitat selection during hibernation. This knowledge could inform local conservation measures related to farming activities.
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The cold compaction of poly (ether ketone ketone) (PEKK) powder was studied by experiments and simulations based on the modified Doraivelu model. Although this model can successfully predict the compaction behavior of metal powders, discussion of the prediction of polymer powders is lacking. Based on the mechanical theory of metal plasticity, the modified Doraivelu model was established by introducing the material parameters m and n. The modified model can predict the compaction density of PEKK powder during cold compaction. A sub-increment method for this constitutive model was then established and implemented into a finite-element model by using the user-defined material subroutine UMAT in ABAQUS/Standard. Consequently, the material parameters of the modified Doraivelu model were identified by an inverse method using the experimental data and simulation results. It was found that when m = 0, n = 4, and the initial relative density was 0.4485, the simulation results were the closest to the experimental ones.
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Industrial pipework maintenance inspection can be automated through machine vision-based effusion monitoring. However, colorless effusions such as water can be difficult to detect in a complex industrial environment due to weak illumination and poor visibility of the background. This paper deploys the reflective characteristics of effusion and its lower temperature compared to the environment in order to develop an automatic inspection system for power plant pipeworks' maintenance. Such a system is aimed at detecting the colorless fluid effusion based on dual source images and a contour features algorithm. In this respect, a visible light source unit highlights the reflective features of the effusion edge. Meanwhile, high-definition images of the potential effusion are acquired under both visible and infrared lights. A customized image processing procedure extracts the potential effusion features from the infrared image to retrieve the region of interest for segmentation purposes and transfer such information to the visible light image to determine the effusion contour. Finally, a decision-making support tool based on the image contour closure is enabled for classification purposes. The implementation of the proposed system is tested on a real industrial environment. Experimental results show a classification accuracy up to 99%, demonstrating excellent suitability in meeting industrial requirements.