Experimental study on the deterioration of mechanical properties of sandy mudstone under different water-gas interactions.

Based on the water-rock-gas coupling test system, the work combined the scanning electron microscope and XTDIC 3D full-field strain measurement system. The Brazilian splitting test was performed on four groups of sandy mudstone specimens under contrast (CO), mash-gas soaking (MS), water-mash gas soaking (WM), and water-soaking (WS) conditions. The tensile strength, deformation failure, and microscopic characteristics of fractures were studied to reveal the deterioration mechanism of the tensile properties of sandy mudstone under water-gas coupling. The results showed that the uniaxial tensile strength of sandy mudstone specimens under the three soaking conditions was less than that of the contrast conditions. Compared with specimens in the CO group, the tensile strength of specimens in MS-WS groups was reduced; the WS group decreased the most. Specimens changed from brittle failure to plastic failure after soaking. The decrease rate in strength after the peak was consistent with the change trend in tensile strength. It led to a larger localized deformation zone of specimens and more obvious displacement. The deformation localization zone of the WS group was the broadest, with the most intense displacement. Besides, stress concentration first occurred in the submerged part of the WM group. Fractures expanded in the direction of maximum principal strain. The internal pore structure of sandy mudstone specimens in each group changed after soaking. The average porosity, maximum pore area, and probability entropy of specimens in WS-MS groups increased compared to the CO group. The WS group had the largest reduction and the MS group had the smallest. The pre-peak energy storage capacity of sandy mudstone specimens was gradually weakened. Compared with the CO group, that in the WS-MS groups was reduced. The WS group had the greatest reduction, and the MS group had the smallest. The deterioration effect of water on the interior of sandy mudstone was stronger than that of gas. The work is of great significance for understanding the stability of coal and rocks in closed-pit high-gas mines.

Palladium-Catalyzed Tandem Cyclization of Bromoalkynes, Anilines and CO: Access to 1,3-Substituted Maleimides.

A novel palladium-catalyzed three-component carbonylation reaction for the assembly of various 1,3-substituted maleimide derivatives from haloalkynes and simple anilines. The nucleophilic addition reaction of haloalkynes, anilines and CO, and insertion of carbonyl have been achieved sequentially in this reaction. The high chemo- and regioselectivities, as well as no need of expensive ligands or additives further illustrate the synthetic value of this approach.

Machine learning models for predicting the risk factor of carotid plaque in cardiovascular disease.

Introduction: Cardiovascular disease (CVD) is a group of diseases involving the heart or blood vessels and represents a leading cause of death and disability worldwide. Carotid plaque is an important risk factor for CVD that can reflect the severity of atherosclerosis. Accordingly, developing a prediction model for carotid plaque formation is essential to assist in the early prevention and management of CVD. Methods: In this study, eight machine learning algorithms were established, and their performance in predicting carotid plaque risk was compared. Physical examination data were collected from 4,659 patients and used for model training and validation. The eight predictive models based on machine learning algorithms were optimized using the above dataset and 10-fold cross-validation. The Shapley Additive Explanations (SHAP) tool was used to compute and visualize feature importance. Then, the performance of the models was evaluated according to the area under the receiver operating characteristic curve (AUC), feature importance, accuracy and specificity. Results: The experimental results indicated that the XGBoost algorithm outperformed the other machine learning algorithms, with an AUC, accuracy and specificity of 0.808, 0.749 and 0.762, respectively. Moreover, age, smoke, alcohol drink and BMI were the top four predictors of carotid plaque formation. It is feasible to predict carotid plaque risk using machine learning algorithms. Conclusions: This study indicates that our models can be applied to routine chronic disease management procedures to enable more preemptive, broad-based screening for carotid plaque and improve the prognosis of CVD patients.

Palladium-Catalyzed Tandem Nucleophilic Addition/C-H Functionalization of Anilines and Bromoalkynes for the Synthesis of 2-Phenylindoles.

A novel and efficient palladium-catalyzed annulation of anilines with bromoalkynes for the synthesis of 2-phenylindoles has been described. This approach features excellent regio- and stereoselectivities and good functional group tolerance. Preliminary mechanistic studies indicate that anilines undergo anti-nucleophilic addition to bromoalkynes to generate (Z)-N-(2-bromo-1-phenylvinyl) anilines, followed by sequential C-H functionalization to deliver different substituted 2-phenylindoles. This method provides potential applications for the construction of various biologically active compounds.

Palladium-catalyzed acetalization/cyclization of enynones with alcohols: rapid access to functionalized dihaloalkenyl dihydrofurans.

Herein, we report a straightforward method to access alkenyl dihydrofurans via palladium-catalyzed acetalization/annulation from conjugated enynones and alcohols. The reaction undergoes a 5-exo-dig cyclization process, with the formation of four new chemical bonds including two carbon-halogen bonds on the exocyclic alkenyl moiety. Preliminary mechanistic studies suggest that the haloalkyne generated in situ should be involved in this transformation.

Palladium-Catalyzed Enantioselective Cyclization of 1,6-Enynes through Intramolecular Chlorine Transfer as a Novel Strategy for Asymmetric Halopalladation.

Palladium-catalyzed enantioselective cyclization of enynes has contributed significantly to the construction of chiral cyclic molecules. In contrast, the catalytic asymmetric cyclization involving halopalladation remains an unresolved challenge with the inevitable disturbance of the halide ions. Herein, an intramolecular chlorine transfer strategy is used to accomplish the enantioselective chloropalladation cyclization of 1,6-enynes. This reaction provides a redox-neutral approach to a variety of chiral α-chloromethylene-γ-butyrolactones with excellent E selectivity and enantioselectivity. The precisely controlled coordination of palladium with both the in situ generated nucleophilic species and the monodentate phosphoramidite ligand is crucial for enantioselectivity.

Palladium-catalyzed three-component cascade arylthiolation with aryldiazonium salts as S-arylation sources.

A novel and efficient palladium-catalyzed three-component cascade cyclization/arylthiolation has been developed for the assembly of diverse 3-sulfenylindole and 3-sulfenylbenzofuran derivatives from 2-alkynylamines and 2-alkynylphenols, aryldiazonium salts, and Na2S2O3 under aerobic conditions with PEG-200 as an environmentally benign medium. The current study features exceptional functional group tolerance without additional ligands, oxidants or silver salts, and eco-friendly mild reaction conditions. The ionic liquid [C2OHmim]Cl plays a crucial role in this protocol as an environmentally friendly additive. Notably, this procedure represents the first example of the use of aryldiazonium salts as direct S-arylation sources in this type of chemical transformation.

Aspirin inhibits endometrial fibrosis by suppressing the TGF­ß1­Smad2/Smad3 pathway in intrauterine adhesions.

Intrauterine adhesions (IUAs) represent one of the most common diseases in women of reproductive age. Patients with moderate­to­severe IUA can experience a decrease in normal menstrual patterns, amenorrhea and even infertility. At present, the first­line treatment strategies for IUAs in the clinical practice are hysteroscopic transuterine resection of adhesion and postoperative adjuvant therapy, including oestrogen. However, a high recurrence rate of IUAs remains. In recent years, studies have demonstrated that aspirin combined with oestrogen may significantly prevent the postoperative disease recurrence rate, improve endometrial receptivity and improve the conception rate by increasing endometrial blood supply and angiogenesis more effectively. The TGF­ß1­Smad2/Smad3 pathway is one of the important mechanisms involved in endometrial fibrosis. However, whether aspirin can inhibit endometrial fibrosis through the TGF­ß1­Smad2/Smad3 pathway to prevent postoperative re­adhesion remains to be elucidated. The results of the present study suggested that aspirin inhibits endometrial fibrosis by suppressing the TGF­ß1­Smad2/Smad3 pathway, which may provide new hypotheses for the mechanism of action of aspirin in the treatment of IUAs.

Palladium-Catalyzed Cascade Cyclization/Alkynylation Reactions.

Palladium-catalyzed cascade cyclization reactions have witnessed significant improvements in recent years. Among them, palladium-catalyzed cascade cyclization/alkynylation are especially attractive, which can assemble structurally diverse monocyclic, bicyclic, fused polycyclic, and spirocyclic skeletons with excellent chemoselectivities. In this Minireview, palladium-catalyzed cascade cyclization/alkynylation have been summarized and discussed in detail with focus on oxypalladation and aminopalladation-initiated cascade cyclization, intramolecular Heck-type cascade cyclization, carbocyclizations, cascade cyclizations, and other types of cascade cyclization reactions. Some significant and representative synthetic methodologies and their synthetic applications and reaction mechanisms have also been described.

Switchable Reactivity between Vinyl Azides and Terminal Alkyne by Nano Copper Catalysis.

A novel nano copper-catalyzed substrate-dependent chemodivergent transformation of vinyl azides with a terminal alkyne is disclosed. 2,5-Disubstituted pyrroles were selectively obtained in high yield with aryl alkynes and aliphatic alkynes, whereas 2,3,4-trisubstituted pyrroles were formed with silylated alkynes. This switchable method provides a controllable and facile access to both multisubstituted pyrrole scaffolds with high efficiency, excellent regioselectivity, and good functional group compatibility.

Direct Assembly of 4-Substituted Quinolines with Vinyl Azides as a Dual Synthon via C═C and C-N Bond Cleavage.

An unprecedented Zn-promoted selective cleavage of vinyl azides for the synthesis of 4-substituted quinolines is developed. In this conversion, vinyl azides function as a dual synthon via C═C and C-N bond cleavage with two C═C bonds and one C═N bond formation in a one-step manner. The reaction is appreciated for its readily accessible substrates, high step economy, mild conditions, and use of air as the sole oxidant.

Palladium-Catalyzed Oxidative Sulfenylation of Indoles and Related Electron-Rich Heteroarenes with Aryl Boronic Acids and Elemental Sulfur.

An efficient and convenient palladium-catalyzed C-H bond oxidative sulfenylation of indoles and related electron-rich heteroarenes with aryl boronic acids and elemental sulfur has been described. This procedure provides a useful and direct approach for the assembly of a wide range of structurally diverse 3-sulfenylheteroarenes with moderate to excellent yields from simple and readily available starting materials. Moreover, this synthetic protocol is suitable for N-protected and unprotected indoles. Notably, the construction of two C-S bonds in one step was also achieved in this transformation.

Assembly of 3-Sulfenylbenzofurans and 3-Sulfenylindoles by Palladium-Catalyzed Cascade Annulation/Arylthiolation Reaction.

A novel and efficient palladium-catalyzed cascade annulation/arylthiolation reaction has been developed to afford functionalized 3-sulfenylbenzofuran and 3-sulfenylindole derivatives in moderate to good yields from readily available 2-alkynylphenols and 2-alkynylamines in ionic liquids. This protocol provides a valuable synthetic tool for the assembly of a wide range of 3-sulfenylbenzofuran and 3-sulfenylindole derivatives with high atom- and step-economy and exceptional functional group tolerance. Moreover, the employment of ionic liquids under mild reaction conditions makes this transformation green and practical. Furthermore, this approach enriched current C-S bond formation chemistry, making a valuable and practical method in synthetic and medicinal chemistry.

Palladium-catalyzed tandem annulation: a strategy to construct 2,3-difunctionalized benzofuran derivatives in ionic liquids.

An efficient and ecofriendly method for the construction of 2,3-difunctionalized benzofuran derivatives in moderate to good yields from readily available 2-alkynylphenols has been developed. This tandem annulation process, featuring one pot, three steps, good functional group tolerance, and high atom economy, makes this transformation efficient and practical. Moreover, this protocol is scalable, illustrating its potential applications in synthetic and pharmaceutical chemistry.

Evolutionary dynamics of ecological niche in three Rhinogobio fishes from the upper Yangtze River inferred from morphological traits.

In the past decades, it has been debated whether ecological niche should be conserved among closely related species (phylogenetic niche conservatism, PNC) or largely divergent (traditional ecological niche theory and ecological speciation) and whether niche specialist and generalist might remain in equilibrium or niche generalist could not appear. In this study, we employed morphological traits to describe ecological niche and test whether different niche dimensions exhibit disparate evolutionary patterns. We conducted our analysis on three Rhinogobio fish species (R. typus,R. cylindricus, and R. ventralis) from the upper Yangtze River, China. Among the 32 measured morphological traits except body length, PCA extracted the first four principal components with their loading scores >1.000. To find the PNC among species, Mantel tests were conducted with the Euclidean distances calculated from the four principal components (representing different niche dimensions) against the pairwise distances calculated from mitochondrial cytochrome b sequence variations. The results showed that the second and the third niche dimension, both related to swimming ability and behavior, exhibited phylogenetic conservatism. Further comparison on niche breadth among these three species revealed that the fourth dimension of R. typus showed the greatest width, indicating that this dimension exhibited niche generalism. In conclusion, our results suggested that different niche dimensions could show different evolutionary dynamic patterns: they may exhibit PNC or not, and some dimensions may evolve generalism.

Palladium-catalyzed cascade annulation to construct functionalized ß- and γ-lactones in ionic liquids.

A highly efficient and mild palladium-catalyzed, one-pot, four-step cascade annulation has been developed to afford functionalized ß- and γ-lactones in moderate to good yields with high regio- and diastereoselectivities in ionic liquids. The employment of ionic liquids under mild reaction conditions makes this transformation green and practical. Especially, this reaction provided a novel and convenient methodology for the construction of naturally occurring biologically active ß- and γ-lactones.

Novel palladium-catalyzed cascade carboxylative annulation to construct functionalized γ-lactones in ionic liquids.

A novel palladium-catalyzed, one-pot, four-step cascade method has been developed to afford functionalized γ-lactones in moderate to good yields. This novel and general methodology represents a rare instance of carbonylation of the C(sp(3))-palladium bond.

Palladium-catalyzed coupling of alkynes with unactivated alkenes in ionic liquids: a regio- and stereoselective synthesis of functionalized 1,6-dienes and their analogues.

A palladium-catalyzed regio- and stereoselective intermolecular tandem reaction of alkynes and unactivated 1,6-enols in ionic liquids is described, providing a practical, efficient, and versatile method for the synthesis of functionalized 1,6-dienes in moderate to good yields. The present reaction has high functional-group tolerance and gives products on a gram scale. Mechanistic studies indicate that the reaction might proceed via a chain-walking mechanism.

A chiral mixed metal-organic framework based on a Ni(saldpen) metalloligand: synthesis, characterization and catalytic performances.

A three-dimensional (3D) chiral mixed metal-organic framework [Cd4Cl(Ni-L)3(Ni-HL)(H2O)6(DMF)]·4DMF (CMOF 1) based on a new enantiopure dicarboxyl-functionalized Ni(saldpen) metalloligand Ni-H2L and a novel tetranuclear cadmium cluster [Cd4Cl(CO2)7(CO2H)] has been synthesized and characterized by elemental analyses, IR and UV-vis spectra, thermogravimetric analysis, nitrogen and carbon dioxide adsorption, powder and single-crystal X-ray diffractions. Each tetranuclear-cadmium cluster in 1 is linked by eight Ni-L ligands, and each Ni-L ligand is linked by two tetranuclear-cadmium clusters to generate a 3D framework with 1D open channels (∼1.1 × 0.9 nm(2)) along the b-axis. Based on its good stability, permanent porosity, Lewis acid sites and moderate uptake for CO2, 1 can be used as a self-supported heterogeneous catalyst for the synthesis of optically active propylene carbonate by asymmetric cycloaddition of CO2 with racemic propylene oxide under relatively mild conditions.

Effects of environmental factors on natural reproduction of the four major Chinese carps in the Yangtze River, China.

The four major Chinese carps are commercially important fish species with high production in China. However, their recruitment decreased sharply in the Yangtze River since the late 20(th) century. In the present study, to reveal the relationships between spawning activities of the four species and environmental factors, drifting eggs were collected at Yidu City, in the middle reaches of the Yangtze River, from May to July each year between 2005 and 2010. Classification and regression trees (CART) analysis was applied to identify the key factors associated with spawning activities of the four carp species. Twelve predictor variables (hydrological and meteorological variables) and one response variable (egg presence or number of egg) were included in the CART. Our CART analysis showed that water temperature and the diurnal increase of water level were the two most significant factors for the spawning activities. When water temperature was between 18°C and 24°C, especially in association with the diurnal increase of water level greater than 0.55 m·d(-1), spawning activities was always favored. Unlike the hydrological factors, meteorological factors seemed to have no influence on initiating the spawning activities. The density of drifting eggs of the four species was mainly influenced by the diurnal variation of water level, the diurnal variation of water discharge, water temperature, humidity, and air pressure. We then related our results to the ecological regulation of the Three Gorge Reservoir in the middle reaches of the Yangtze River. We suggested that, when water temperature was between 18-24°C from May to July, to ensure the successful spawning of the four carp species, the ecological regulation should be managed to create flood peaks and make the diurnal increase of water level greater than 0.55 m·d(-1).