Unsaturated bi-heterometal clusters in metal-vacancy sites of 2D MoS2 for efficient hydrogen evolution

The valence states and coordination structures of doped heterometal atoms in two-dimensional(2D)nanomaterials lack predictable regulation strategies.Hence,a robust method is proposed to form unsaturated heteroatom clusters via the metal-vacancy restraint mechanism,which can precisely regulate the bonding and valence state of heterometal atoms doped in 2D molybdenum disulfide.The unsaturated valence state of heterometal Pt and Ru cluster atoms form a spatial coordination structure with Pt–S and Ru–O–S as catalytically active sites.Among them,the strong binding energy of negatively charged suspended S and O sites for H+,as well as the weak adsorption of positively charged unsaturated heterometal atoms for H*,reduces the energy barrier of the hydrogen evolution reaction proved by theoretical calculation.Whereupon,the electrocatalytic hydrogen evolution performance is markedly improved by the ensemble effect of unsaturated heterometal atoms and highlighted with an overpotential of 84 mV and Tafel slope of 68.5 mV dec^(−1).In brief,this metal vacancy-induced valence state regulation of heterometal can manipulate the coordination structure and catalytic activity of heterometal atoms doped in the 2D atomic lattice but not limited to 2D nanomaterials.

Surrogate modeling for unsaturated infiltration via the physics and equality-constrained artificial neural networks

Machine learning(ML)provides a new surrogate method for investigating groundwater flow dynamics in unsaturated soils.Traditional pure data-driven methods(e.g.deep neural network,DNN)can provide rapid predictions,but they do require sufficient on-site data for accurate training,and lack interpretability to the physical processes within the data.In this paper,we provide a physics and equalityconstrained artificial neural network(PECANN),to derive unsaturated infiltration solutions with a small amount of initial and boundary data.PECANN takes the physics-informed neural network(PINN)as a foundation,encodes the unsaturated infiltration physical laws(i.e.Richards equation,RE)into the loss function,and uses the augmented Lagrangian method to constrain the learning process of the solutions of RE by adding stronger penalty for the initial and boundary conditions.Four unsaturated infiltration cases are designed to test the training performance of PECANN,i.e.one-dimensional(1D)steady-state unsaturated infiltration,1D transient-state infiltration,two-dimensional(2D)transient-state infiltration,and 1D coupled unsaturated infiltration and deformation.The predicted results of PECANN are compared with the finite difference solutions or analytical solutions.The results indicate that PECANN can accurately capture the variations of pressure head during the unsaturated infiltration,and present higher precision and robustness than DNN and PINN.It is also revealed that PECANN can achieve the same accuracy as the finite difference method with fewer initial and boundary training data.Additionally,we investigate the effect of the hyperparameters of PECANN on solving RE problem.PECANN provides an effective tool for simulating unsaturated infiltration.

Wetting front migration model of ion-adsorption rare earth during the multi-hole unsaturated liquid injection

In the process of ion-adsorption rare earth ore leaching,the migration characteristics of the wetting front in multi-hole injection holes and the influence of wetting front intersection effect on the migration distance of wetting fronts are still unclear.Besides,wetting front migration distance and leaching time are usually required to optimize the leaching process.In this study,wetting front migration tests of ionadsorption rare earth ores during the multi-hole fluid injection(the spacing between injection holes was 10 cm,12 cm and 14 cm)and single-hole fluid injection were completed under the constant water head height.At the pre-intersection stage,the wetting front migration laws of ion-adsorption rare earth ores during the multi-hole fluid injection and single-hole fluid injection were identical.At the postintersection stage,the intersection accelerated the wetting front migration.By using the Darcy’s law,the intersection effect of wetting fronts during the multi-hole liquid injection was transformed into the water head height directly above the intersection.Finally,based on the Green-Ampt model,a wetting front migration model of ion-adsorption rare earth ores during the multi-hole unsaturated liquid injection was established.Error analysis results showed that the proposed model can accurately simulate the infiltration process under experimental conditions.The research results enrich the infiltration law and theory of ion-adsorption rare earth ores during the multi-hole liquid injection,and this study provides a scientific basis for optimizing the liquid injection well pattern parameters of ion-adsorption rare earth in situ leaching in the future.

Serum bile acid and unsaturated fatty acid profiles of non-alcoholic fatty liver disease in type 2 diabetic patients

BACKGROUND The understanding of bile acid(BA)and unsaturated fatty acid(UFA)profiles,as well as their dysregulation,remains elusive in individuals with type 2 diabetes mellitus(T2DM)coexisting with non-alcoholic fatty liver disease(NAFLD).Investigating these metabolites could offer valuable insights into the pathophy-siology of NAFLD in T2DM.AIM To identify potential metabolite biomarkers capable of distinguishing between NAFLD and T2DM.METHODS A training model was developed involving 399 participants,comprising 113 healthy controls(HCs),134 individuals with T2DM without NAFLD,and 152 individuals with T2DM and NAFLD.External validation encompassed 172 participants.NAFLD patients were divided based on liver fibrosis scores.The analytical approach employed univariate testing,orthogonal partial least squares-discriminant analysis,logistic regression,receiver operating characteristic curve analysis,and decision curve analysis to pinpoint and assess the diagnostic value of serum biomarkers.RESULTS Compared to HCs,both T2DM and NAFLD groups exhibited diminished levels of specific BAs.In UFAs,particular acids exhibited a positive correlation with NAFLD risk in T2DM,while theω-6:ω-3 UFA ratio demonstrated a negative correlation.Levels ofα-linolenic acid andγ-linolenic acid were linked to significant liver fibrosis in NAFLD.The validation cohort substantiated the predictive efficacy of these biomarkers for assessing NAFLD risk in T2DM patients.CONCLUSION This study underscores the connection between altered BA and UFA profiles and the presence of NAFLD in individuals with T2DM,proposing their potential as biomarkers in the pathogenesis of NAFLD.

Thermal-water-salt coupling process of unsaturated saline soil under unidirectional freezing

Salinization and desertification are closely related to water-salt migration caused by a temperature gradient.Based on the Darcy Law of unsaturated soils,the law of energy conservation and the law of mass conservation,the thermal-water-salt coupling mathematical model of unsaturated frozen saline soil was established.The model considered the latent heat of phase change,crystallization impedance,crystallization consumption and complete precipitation of solute crystallization in ice.In order to verify the rationality of the model,the unidirectional freezing test of unsaturated saline soil was carried out in an open system with no-pressure water supplement to obtain the spatial distribution of temperature,moisture and salt in the saline soil.Finally,numerical simulations are implemented with the assistance of COMSOL Multiphysics.Validation of the model is illustrated by comparisons between the simulation and experimental data.The results demonstrated that the temperature within saline soil changes with time and can be divided into three stages,namely quick freezing stage,transitional stage and stable stage.The water and salt contents in the freezing zone are layered,with peak values at the freezing front.The coupled model could reveal the heat-mass migration mechanism of unsaturated frozen saline soil and dynamically describe the freezing depth and the movement law of the freezing front,ice and salt crystal formation mechanism,and the change law of thermal conductivity and permeability coefficient.

Two-dimensional plane strain consolidation of unsaturated soils considering the depth-dependent stress

In practical engineering,the total vertical stress in the soil layer is not constant due to stress diffusion,and varies with time and depth.Therefore,the purpose of this paper is to investigate the effect of stress diffusion on the two-dimensional(2D)plane strain consolidation properties of unsaturated soils when the stress varies with time and depth.A series of semi-analytical solutions in terms of excess pore air and water pressures and settlement for 2D plane strain consolidation of unsaturated soils can be derived with the joint use of Laplace transform and Fourier sine series expansion.Then,the inverse Laplace transform of the semi-analytical solution is given in the time domain using a self-programmed code based on Crump’s method.The reliability of the obtained solutions is proved by the degeneration.Finally,the 2D plots of excess pore pressures and the curves of settlement varying with time,considering different physical parameters of unsaturated soil stratum and depth-dependent stress,are depicted and analyzed to study the 2D plane strain consolidation properties of unsaturated soils subjected to the depthdependent stress.

A Numerical Simulation Study of Temperature and Pressure Effects on the Breakthrough Pressure of CO_(2)in Unsaturated Low-permeability Rock Core

Gas breakthrough pressure is a key parameter to evaluate the sealing capacity of caprock,and it also plays important roles in safety and capacity of CO_(2)geological storage.Based on the published experimental results,we present numerical simulations on CO_(2)breakthrough pressure in unsaturated low-permeability rock under 9 multiple P-T conditions(which can keep CO_(2)in gaseous,liquid and supercritical states)and thus,a numerical method which can be used to accurately predict CO_(2)breakthrough pressure on rock-core scale is proposed.The simulation results show that CO_(2)breakthrough pressure and breakthrough time are exponential correlated with P-T conditions.Meanwhile,pressure has stronger effects on experimental results than that of temperature.Moreover,we performed sensitivity studies on the pore distribution indexλ(0.6,0.7,0.8,and 0.9)in van Genuchten-Muale model.Results show that with the increase ofλ,CO_(2)breakthrough pressure and breakthrough time both show decreasing trends.In other words,the larger the value ofλis,the better the permeability of the caprock is,and the worse the CO_(2)sealing capacity is.The numerical method established in this study can provide an important reference for the prediction of gas breakthrough pressure on rock-core scale and for related numerical studies.

Enabling heterogeneous catalysis to achieve carbon neutrality: Directional catalytic conversion of CO_(2) into carboxylic acids

The increase in anthropogenic carbon dioxide(CO_(2))emissions has exacerbated the deterioration of the global environment,which should be controlled to achieve carbon neutrality.Central to the core goal of achieving carbon neutrality is the utilization of CO_(2) under economic and sustainable conditions.Recently,the strong need for carbon neutrality has led to a proliferation of studies on the direct conversion of CO_(2) into carboxylic acids,which can effectively alleviate CO_(2) emissions and create high-value chemicals.The purpose of this review is to present the application prospects of carboxylic acids and the basic principles of CO_(2) conversion into carboxylic acids through photo-,electric-,and thermal catalysis.Special attention is focused on the regulation strategy of the activity of abundant catalysts at the molecular level,inspiring the preparation of high-performance catalysts.In addition,theoretical calculations,advanced technologies,and numerous typical examples are introduced to elaborate on the corresponding process and influencing factors of catalytic activity.Finally,challenges and prospects are provided for the future development of this field.It is hoped that this review will contribute to a deeper understanding of the conversion of CO_(2) into carboxylic acids and inspire more innovative breakthroughs.

Pre-pregnant Overweight Interacts with ADIPOQ Genetic Variants to Influence Polyunsaturated Fatty Acids in Human Milk

Adiponectin,a specific hormone protein secreted by adipocytes,is a protective factor in the human body and has attracted great attention due to its anti-obesity activity[1,2].The adiponectin gene(ADIPOQ),which is located on human chromosome 3q27,is a single-copy gene.Various single-nucleotide polymorphisms(SNPs)of the human ADIPOQ play an important role in energy balance and are associated with body mass index(BMI)and obesity[3,4].Longchain polyunsaturated fatty acids(LC-PUFAs)have been identified to exert an important role during the first 1,000 days of life on infant growth,neurodevelopment,and visual acuity.Fatty acids,such asα-linoleic acid(ALA,C18:3n-3)and linoleic acid(LA,C18:2n-6),which cannot be synthesized de novo from other lipids,are necessary for biological reactions.Some fatty acids such as docosahexaenoic acid(DHA,C22:6n-3)and eicosapentaenoic acid(EPA,C20:5n-3)can be synthesized in neonates from their precursors(LA and ALA).Because of the very low conversion rates in the neonatal liver,it is crucial to provide adequate LC-PUFAs in the diet from early infancy.

Ultralow-Energy-Barrier H_(2)O_(2)Dissociation on Coordinatively Unsaturated Metal Centers in Binary Ce-Fe Prussian Blue Analogue for Efficient and Stable Photo-Fenton Catalysis

The low intrinsic activity of Fenton catalytic site and high demand for light-energy input inhibit the organic-pollution control efficiency of photo-Fenton process.Here,through structural design with density functional theory(DFT)calculations,Ce is predicted to enable the construction of coordinatively unsaturated metal centers(CUCs)in Prussian blue analogue(PBA),which can strongly adsorb H_(2)O_(2)and donate sufficient electrons for directly splitting the O-O bond to produceOH.Using a substitution-co-assembly strategy,binary Ce-Fe PBA is then prepared,which rapidly degrades sulfamethoxazole with the pseudo-first-order kinetic rate constant exceeding reported values by 1-2 orders of magnitude.Meanwhile,the photogenerated electrons reduce Fe(Ⅲ)and Ce(Ⅳ)to promote the metal valence cycle in CUCs and make sulfamethoxazole degradation efficiency only lose 6.04%in 5 runs.Overall,by introducing rare earth metals into transition metal-organic frameworks,this work guides the whole process for highly active CUCs from design and construction to mechanism exploration with DFT calculations,enabling ultrafast and stable photo-Fenton catalysis.

Multiusers Parallel Competitive Channel Protocol Based on Unsaturated Service

In order to enhance the area throughput of next generation wireless local area network(WLAN)in high density scenarios,orthogonal frequency division multiple access(OFDMA)has been adopted as one of the key technologies in the next generation WLAN communication standards.However,the performance of the existing media access control(MAC)degrades significantly under unsaturated services.Therefore,this paper proposes a multi-user parallel contention channel MAC(MU-MAC)based on unsaturated services,which can effectively reduce the channel access conflict and improve the OFDMA access efficiency of cluster member nodes.On this basis,MU-MAC is enhanced for the spatial clustering group(SCG)formation protocol and support for the unsaturated service characteristics.Further,the optimal access radius when the service is in a non-saturated state is analyzed to make the relevant theoretical analysis more generally,and the expressions for the throughput and area throughput of the proposed protocol are modeled and derived.The simulation results verify the correctness of the theoretical analysis and the efficiency of the protocol performance.The results show that MU-MAC outperforms IEEE 802.11ax and OMAX protocol in area throughput by 40.72%and 104.15%,respectively.

Fractional derivative statistical damage model of unsaturated expansive soil based on unified hydraulic effect

Unsaturated expansive soil is widely distributed in China and has complex engineering properties.This paper proposes the unified hydraulic effect shear strength theory of unsaturated expansive soil based on the effective stress principle,swelling force principle,and soil–water characteristics.Considering the viscoelasticity and structural damage of unsaturated expansive soil during loading,a fractional hardening–damage model of unsaturated expansive soil was established.The model parameters were established on the basis of the proposed calculation method of shear strength and the triaxial shear experiment on unsaturated expansive soil.The proposed model was verified by the experimental data and a traditional damage model.The proposed model can satisfactorily describe the entire process of the strain-hardening law of unsaturated expansive soil.Finally,by investigating the damage variables of the proposed model,it was found that:(a)when the values of confining pressure and matric suction are close,the coupling of confining pressure and matric suction contributes more to the shear strength;(b)there is a damage threshold for unsaturated expansive soil,and is mainly reflected by strength criterion of infinitesimal body;(c)the strain hardening law of unsaturated expansive soil is mainly reflected by fractional derivative operator.

The capillary pressure curves from upscaling interfacial and unsaturated flows in porous layers with vertical heterogeneity

We provide the capillary pressure curves p_(c)(s)as a function of the effective saturation s based on the theoretical framework of upscaling unsaturated flows in vertically heterogeneous porous layers proposed recently(Z.Zheng,Journal of Fluid Mechanics,950,A17,2022).Based on the assumption of vertical gravitational-capillary equilibrium,the saturation distribution and profile shape of the invading fluid can be obtained by solving a nonlinear integral-differential equation.The capillary pressure curves p_(c)(s)can then be constructed by systematically varying the injection rate.Together with the relative permeability curves k_(rn)(s)that are already obtained.One can now provide quick estimates on the overall behaviours of interfacial and unsaturated flows in vertically-heterogeneous porous layers.

Characterization of Unsaturated Polyester Filled with Waste Coconut Shells, Walnut Shells, and Carbon Fibers

This study aims to evaluate the erosion behavior and the hardness of hybrid composites made of varying amounts of coconut shells,walnut shells,and carbonfibers dispersed in a polyester matrix.MINITAB(L16)Taguchi experiments were used to determine the optimal combination of parameters.In particular,an erosion device con-sisting of a motor with a constantflow rate of 45 L/min,a pump with a diameter of 40 mm,a nozzle with a dia-meter of 5 mm,and a tank made of“perspex glass”55 cm long,30 cm tall,and 25 cm wide was used.The tests were conducted by varying the sample-to-nozzle distance,the pattern angle,and the sand particle size.The results have revealed that the presence of 7.5%by weight of waste coconut shell,for conditions corresponding to 90°angle,sand size 425μm,stand distance 30 cm,gives the best wear resistance(3.04×10^(-5) g/g).Thefiller content and sand particle size affect the erosive rate,with the angle playing a secondary role.The distance between the sample and the nozzle has a weaker effect on erosive wear.The hardness results show that the models(UP-5%carbonfiber-2.5-3.5-4.5-5.5-6.5-7.5 wt.%waste coconut shell)give the best values for prayer compared to the samples(UP-5 wt.%carbonfiber-2.5-3.5-4.5-5.5-6.5-7.5 wt.%waste walnut shell).

Chemoselective Catalytic Hydrogenation of α,β-Unsaturated Ketones and α,β-Unsaturated Carboxylic Esters

The effect of catalysts P-2 00-Ni(Nickel boride) and P-2 00-Ni-M(M: Co, Fe, Cu, Sn), prepared by adopting a modified recipe, on the chemoselective hydrogenation of carbon carbon double bonds in α,β- unsaturated ketones, and the activity of catalysts P-1.80-Ni, P-2 00-Ni or P-1.80(2 00) -Ni-M(M: Pd, Co, Cu) in the selective hydrogenation of carbon carbon double bonds in α,β-unsaturated carboxylic esters, were investigated systematically. According to the experimental results, the selectivities of these catalysts toward the hydrogenation of the carbon carbon double bonds of α,β-unsaturated keones or α,β-unsaturated carboxylic esters are 96%—100% or 100%, respectively.

Doebner condensation in ionic liquids [Bmim]BF_4 and [Bpy]BF_4 to synthesize α,β-unsaturated carboxylic acid

Ionic liquids [Bmim]BF4 and [Bpy]BF4 were employed as environmentally benign media in Doebner condensation to synthesize α, β-unsaturated carboxylic acid. The good results showed that [Bmim]BF4 and [Bpy]BF4 were efficient media for Doebner condensation, which could be recycled easily. The highest yields could reach 93% and 90% in [Bmim]BF4 and [Bpy]BF4, respectively.

Using Electrodeposition of Carboxylated Chitosan for Green Preparation of Copper Nanoclusters and Nanocomposite Films

On the basis of coordinated electrodeposition of carboxylated chitosan(CCS),we presented a green method to prepare Cu NCs and Cu NCs/CCS nanocomposite films.The method shows a range of benefits,such as the convenient and eco-friendly process,mild conditions,and simple post-treatment.The experimental results reveal that a homogeneous deposited film(Cu NCs/CCS nanocomposite film)is generated on the Cu plate(the anode)after electrodeposition,which exhibits an obvious red florescence.The results from TEM observation suggest there are nanoparticles(with the average particle size of 2.3 nm)in the deposited film.Spectral analysis results both demonstrate the existence of Cu NCs in the deposited film.Moreover,the Cu NCs/CCS film modified electrode is directly created through electrodeposition of CCS,which enables promising application in the electrochemical sensing.By means of fluorescence properties of Cu NCs,the Cu NCs/CCS film also owns the potential in fluorescence detection.Therefore,this work builds a novel method for the green synthesis of Cu NCs,meanwhile it offers a convenient and new electrodeposition strategy to prepare polysaccharide-based Cu NCs nanocomposites for uses in functional nanocomposites and bioelectronic devices.

Carboxyl Ester Lipase Protects Against Metabolic Dysfunction-Associated Steatohepatitis by Binding to Fatty Acid Synthase

Carboxyl ester lipase(CEL),a pivotal enzyme involved in lipid metabolism,is recurrently mutated in obese mice.Here,we aimed to elucidate the functional significance,molecular mechanism,and therapeutic potential of CEL in metabolic dysfunction-associated steatohepatitis(MASH).Hepatocyte-specific carboxyl ester lipase gene(Cel)knockout(Cel^(DHEP))and wildtype(WT)littermates were fed with cholinedeficient high-fat diet(CD-HFD)for 16 weeks,or methionine-and choline-deficient diet(MCD)for three weeks to induce MASH.Liquid chromatography–mass spectrometry and co-immunoprecipitation were employed to identify the downstream targets of CEL.CD-HFD/MCD-fed WT mice received intravenous injections of CEL-adeno-associated viral,serotype 8(AAV8)to induce specific overexpression of CEL in the liver.We observed a decrease in CEL protein levels in MASH induced by CD-HFD or MCD in mice.Cel^(DHEP) mice fed with CD-HFD or MCD exhibited pronounced hepatic steatosis,inflammation,lipid peroxidation,and liver injury compared to WT littermates,accompanied by increased hepatic nuclear factor kappa-light-chain-enhancer of activated B cell(NF-jB)activation.Consistently,Cel knockdown in mouse primary hepatocytes and AML12 cells aggravated lipid accumulation and inflammation,whereas CEL overexpression exerted the opposite effect.Mechanistically,CEL directly bound to fatty acid synthase(FASN),resulting in reduced FASN SUMOylation,which in turn promoted FASN degradation through the proteasome pathway.Furthermore,inhibition of FASN ameliorated hepatocyte lipid accumulation and inflammation induced by Cel knockdown in vivo and in vitro.Hepatocyte-specific CEL overexpression using AAV8-Cel significantly mitigated steatohepatitis in mice fed with CD-HFD or MCD.CEL protects against steatohepatitis development by directly interacting with FASN and suppressing its expression for de novo lipogenesis.CEL overexpression confers a therapeutic benefit in steatohepatitis.

Synthesis and Characterization of Novel Fluoroalkyl Unsaturated Multi-carboxylic Acid Esters

A series of fluorinated unsaturated esters which can be used as fluorine-containing monomers have been synthesized. The esterification of maleic acid,itaconic acid,and trans-aconitic acid with 1, 1, 2, 2-tetrahydroperfluorooctanol and 1, 1, 5- octafluoropentanol was carried out, respectively. The objective monomers were obtained by using p-toluene sulfonic acid as catalyst, hydroquinone as the anti-polymerizing agent,toluene as solvent and water carrying agent. The objective products were isolated by column chromatography and characterized by Fourier transform infrared spectroscopy ( FT-IR ) , hydrogen-1 nuclear magnetic resonance ( 1 H NMR) ,fluorine-19 nuclear magnetic resonance ( 19 F NMR) ,and high resolution mass spectrometry ( HRMS) . The yield of the objective products was various from 30% to 85%. The reaction result shows that the esterification of 1, 1, 5 - octafluoropentanol with certain carboxylic acid is more difficult than that of 1,1,2,2-tetrahydroperfluorooctanol.

Carboxylic bacterial cellulose fiber-based hydrogel electrolyte with imidazole-type ionic liquid for dendrite-free zinc metal batteries

Aqueous zinc metal batteries are regarded as the most promising energy storage system due to their advantages of high safety,low cost,and high theoretical capacity.However,the growth of dendrites and the occurrence of side reactions hinder the development of zinc metal batteries.Despite previous attempts to design advanced hydrogel electrolytes,achieving high mechanical performance and ionic conductivity of hydrogel electrolytes has remained challenging.In this work,a hydrogel electrolyte with an ionic crosslinked network is prepared by carboxylic bacterial cellulose fiber and imidazole-type ionic liquid,following by a covalent network of polyacrylamide.The hydrogel electrolyte possesses a superior ionic conductivity of 43.76 mS cm^(−1),leading to a Zn^(2+)migration number of 0.45,and high mechanical performance with an elastic modulus of 3.48 GPa and an elongation at breaking of 38.36%.More importantly,under the anion-coordination effect of the carboxyl group in bacterial cellulose and[BF4]−in imidazole-type ionic liquid,the solvation sheath of hydrated Zn^(2+)ions and the nucleation overpotential of Zn plating are regulated.The results of cycled testing show that the growth of zinc dendrites is effectively inhibited and the generation of irreversible by-products is reduced.With the carboxylic bacterial cellulose-based hydrogel electrolyte,the Zn||Zn symmetric batteries offer good cyclability as well as Zn||Ti batteries.