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.

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).

Copper-Free Resin-Based Braking Materials:A New Approach for Substituting Copper with Fly-Ash Cenospheres in Composites

Copper particles emitted from braking have become a significant source of environmental pollution.However,copper plays a crucial role in resin-based braking materials.Developing high-performance braking materials without copper has become a significant challenge.In this paper,the resin-based braking materials were filled with flyash cenospheres to develop copper-free braking materials.The effects of fly-ash cenospheres on the physical properties,mechanical and friction and wear properties of braking materials were studied.Furthermore,the wear mechanism of copper-free resin-based braking materials filled with fly-ash cenospheres was discussed.The results indicate that the inclusion of fly-ash cenospheres in the braking materials improved their thermal stability,hardness and impact strength,reduced their density,effectively increased the friction coefficient at medium and high temperatures,and enhanced the heat-fade resistance of the braking materials.The inclusion of fly-ash cenospheres contributed to the formation of surface friction film during the friction process of the braking materials,and facilitated the transition of form from abrasive wear to adhesive wear.At 100-350℃,the friction coefficient of the optimal formulation is in the range of 0.57-0.61,and the wear rate is in the range(0.29-0.65)×10^(-7) cm^(3)·N^(-1)·m^(-1),demonstrating excellent resistance to heat-fade and stability in friction coefficient.This research proposes the use of fly-ash cenospheres as a substitute for environmentally harmful and expensive copper in brake materials,which not only improves the performance of braking materials but also reduces their costs.

Copper-Catalyzed C-C(O)C Bond Cleavage of Monoalkylated β-Diketone: Synthesis of α,β-Unsaturated Ketones

A new and simple route for the synthesis of α,β-unsaturated ketones via cleavage of the C-C(O)C single bond of monoalkylated β-diketone has been described. The reaction was catalyzed by copper, a cheap transition metal in a weakly basic medium (K3PO4) at room temperature. To carry out this study, we first had to synthesize the monoalkylated β-diketones 1. Afterwards, α,β-unsaturated ketones 2 were obtained with high yields around 80%. Finally, all the products were characterized by 1H NMR, 13C NMR, and HRMS spectra. .

Water content and modulus relationship of a compacted unsaturated soil

In order to assess the performance of the embankment soil under various climate conditions during the period of service, the modulus behaviour of an unsaturated compacted soil is evaluated using the constant water content triaxial test. Since the water content measurement method is simple and economical and it is used widely in engineering, the soil suction is replaced by the water content and the relationship between the water content and the modulus is developed. The compacted samples are prepared with different compacted water contents, and samples with a similar water content subjected to drying or wetting procedures prior to the triaxial test are also investigated. The effect of the water content and the confining pressure on the modulus is analyzed. The results show that the modulus decreases with the increase in the water content and a power function can be proposed to quantitatively describe the relationship between the modulus and the water content in the range of the measured water content. The modulus increases with the increase in the confining pressure of the compacted soil. However, the effect of the water content on the modulus is more pronounced than that of the confining pressure. This research can be referenced for the compacted embankment soil assessment in-service period.

The Unsaturated Hydraulic Parameters for Aeolian Sand

The water characteristic curve for aeolian sand in two processes of wetting and drying was obtained by the negative water column technique.The values of fitting parameters were calculated according to Van Genuchten formula and the parameters that characterized the prosperities of aeolian sand such as the unsaturated infiltration coefficient and specific water capacity were obtained.The results showed that the water characteristic curve for aeolian sand in wetting process had greater hysteresis quality than ...

MODELING STUDY ON REMOVAL OF NITRATE IN WATER SYSTEM BY BACTERIA TRANSPLANTED IN UNSATURATED ZONE

With a view to treating the nitrate pollution in water systems,this article presents a novel method for eliminating nitrate from wastewater by bacteria through unsaturated zone. First,highly efficient denitrifiers suitable for underground environment have been studied based on the biochemical characterization and denitrifying mechanism of microorganisms. Then the nitrate-eliminating modeling study in soil columns was carried out with the obtained denitrifier. The results show that the nitrate-eeliminating efficiency can reach 98%,so it has practical value in controlling nitrate pollution in water systems.

Distinctive roles of unsaturated and saturated fatty acids in hyperlipidemic pancreatitis

AIM: To investigate how the saturated and unsaturated fatty acid composition influences the susceptibility of developing acute pancreatitis. METHODS: Primary pancreatic acinar cells were treated with low and high concentrations of different saturated and unsaturated fatty acids, and changes in the cytosolic Ca2+ signal and the expression of protein kinase C(PKC) were measured after treatment. RESULTS: Unsaturated fatty acids at high concentrations, including oleic acid, linoleic acid, palmitoleic acid, docosahexaenoic acid, and arachidonic acid, induced a persistent rise in cytosolic Ca2+ concentrations in acinar cells. Unsaturated fatty acids at low concentrations and saturated fatty acids, including palmitic acid, stearic acid, and triglycerides, at low and high concentrations were unable to induce a rise in Ca2+ concentrations in acinar cells. Unsaturated fatty acids at high concentrations but not saturated fatty acids induced intra-acinar cell trypsin activation and cell damage and increased PKC expression.CONCLUSION: At sufficiently high concentrations, unsaturated fatty acids were able to induce acinar cells injury and promote the development of pancreatitis. Unsaturated fatty acids may play a distinctive role in the pathogenesis of pancreatitis through the activation of PKC family members.

Expression profile of polyunsaturated fatty acids in colorectal cancer

AIM:To investigate the relationship between the metabolism of polyunsaturated fatty acids(PUFAs)andtumor-associated factors for predicting the outcome of colorectal carcinoma(CRC)in Chinese patients.METHODS:Fresh-frozen malignant and normal tissues from 82 Chinese patients with CRC were analyzed for PUFA composition using gas-liquid chromatography.The levels of vascular endothelial growth factor(VEGF),cyclooxygenase-2(COX-2),prostaglandin E2 and platelet-derived growth factor(PDGF)were measured by enzyme-linked immunosorbent assay,and the levels of VEGF,p53 and Ki-67 were measured by immunohistochemistry.RESULTS:In malignant tissue,compared with normal tissue,the levels of totalω-6 PUFAs(24.64%±3.41%vs 26.77%±3.37%,P=0.00)and linoleic acid(LA)(15.46%±3.51%vs 18.30%±2.83%,P<0.01)were lower,whereas the levels of totalω-3 PUFAs(1.58%±0.74%vs 1.35%±0.60%,P<0.01)and dihomo-gamma-linolenic acid(DGLA)(1.32%±0.69%vs 0.85%±0.29%,P<0.01)were significantly higher.The ratios of arachidonic acid(AA)/LA(0.53±0.22 vs0.42±0.19,P<0.01)and AA/totalω-6 PUFAs(0.31±0.09 vs 0.27±0.10,P<0.01)were also significantly higher in malignant tissue.The levels of PDGF(353.10±148.85 pg/m L vs 286.09±104.91 pg/m L,P<0.01),COX-2(125.21±70.29 ng/m L vs 67.06±42.22 ng/m L,P<0.01)and VEGF(357.11±128.76 pg/m L vs211.38±99.47 pg/m L,P<0.01)were also higher in malignant tissue compared to normal tissue.COX-2was inversely correlated with LA(R=-0.3244,P<0.05)and positively correlated with AA/totalω-6 PUFAs(R=0.3083,P<0.05)and AA/LA(R=0.3001,P<0.05).The tissue level of LA was highest in poorly differentiated tumors(19.9%±6.3%,P<0.05),while the ratio of AA/ω-3 PUFAs was lowest in these tumors(10.8±2.6,P<0.05).In VEGF-positive tumors,the level of LA was higher(16.2%±3.7%vs 13.9%±2.7%,P<0.01),while the AA/ω-3PUFA,AA/ω-6 PUFA,and AA/LA ratios were lower than in VEGF-negativetumors(5.0±1.8 vs 6.7±3.3,0.30±0.09 vs 0.34±0.09,0.50±0.21 vs 0.61±0.21,P<0.01).CONCLUSION:The metabolism of PUFAs may playan important role in the evolution of inflammationdriven tumorigenesis in CRC and may be considered apotential marker for prognosis.