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.

An improved creep model for unsaturated reticulated red clay

Establishment of a creep model is an important method to analyze the relationship between soil creep deformation and time,and the element model is widely used for studying soil creep.However,the element creep model is employed for fitting saturated soil,and the mechanical element model is generally linear,which cannot well fit the nonlinear deformation of the soil with time in practice.The creep process of the soil is not only time-dependent,but also related to the deviatoric stress level.Therefore,the fractional calculus theory and a parameter n reflecting the effect of deviatoric stress level on the creep properties of the soil were introduced into the element model,and the fractional qBurgers creep model was established by using the fractional Koeller dashpot and Caputo fractional calculus.The proposed model was used to fit the triaxial test data of reticulated red clay under different net confining pressures and matric suctions by unsaturated triaxial apparatus.The proposed model can well describe the nonlinearity of unsaturated reticulated red clay,has memory and global correlation to the creep development process of unsaturated reticulated red clay,and has clear physical meaning.The functional relationships of the model parameters with the matric suction,net confining pressure and deviatoric stress level were deduced,so that the creep curves of unsaturated reticulated red clay can be obtained for any conditions,which is of great value for the study of unsaturated soils.

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.

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.

Stability analysis of unsaturated soil slope during rainfall infiltration using coupled liquid-gas-solid three-phase model

Generally, most soil slope failures are induced by rainfall infiltration, a process that involves interactions between the liquid phase, gas phase,and solid skeleton in an unsaturated soil slope. In this study, a loosely coupled liquid-gas-solid three-phase model, linking two numerical codes,TOUGH2/EOS3, which is used for water-air two-phase flow analysis, and FLAC^(3D), which is used for mechanical analysis, was established. The model was validated through a documented water drainage experiment over a sandy column and a comparison of the results with measured data and simulated results from other researchers. The proposed model was used to investigate the features of water-air two-phase flow and stress fields in an unsaturated soil slope during rainfall infiltration. The slope stability analysis was then performed based on the simulated water-air two-phase seepage and stress fields on a given slip surface. The results show that the safety factor for the given slip surface decreases first, then increases, and later decreases until the rainfall stops. Subsequently, a sudden rise occurs. After that, the safety factor decreases continually and reaches its lowest value, and then increases slowly to a steady value. The lowest value does not occur when the rainfall stops, indicating a delayed effect of the safety factor. The variations of the safety factor for the given slip surface are therefore caused by a combination of pore-air pressure, matric suction, normal stress, and net normal stress.

Creep model for unsaturated soils in sliding zone of Qianjiangping landslide

The mechanical behavior of sliding zone soils plays a significant role in landslide. In general, the sliding zone soils are basically in unsaturated state due to rainfall infiltration and reservoir water level fluctuation. Meanwhile, a large number of examples show that the deformation processes of landslides always take a long period of time, indicating that landslides exhibit a time-dependent property. Therefore, the deforma- tion of unsaturated soils of landslide involves creep behaviors. In this paper, the Burgers creep model for unsaturated soils under triaxial stress state is considered based on the unsaturated soil mechanics. Then, by curve fitting using the least squares method, creep parameters in different matric suction states are obtained based on the creep test data of unsaturated soils in the sliding zones of Qianjiangping landslide. Results show that the predicted results are in good agreement with the experimental data, Finally, to fur- ther explore the creep characteristics of the unsaturated soils in sliding zones, the relationships between parameters of the model and matric suction are analyzed and a revised Burgers creep model is developed correspondingly. Simulations on another group of test data are performed by using the modified Burgers creep model and reasonable results are observed,

PROPERTIES AND MORPHOLOGY OF UNSATURATED POLYESTER/ACRYLATE-TERMINATED POLYURETHANE/ORGANO-MONTMORILLONITE NANOCOMPOSITES

Unsaturated polyester resin （UPR）/acrylate-terminated polyurethane （ATPU）/organo-modified montmorillonite （OMMT） nanocomposites were prepared by the in situ intercalative polymerization method. Samples were prepared by the sequential mixing, i.e. mixture of the ATPU and styrene （S） and OMMT were prepared in the first step; UPR was then added to the pre-intercalates of ATPU/S/OMMT. Results indicate that the mechanical properties and thermal properties of UPR/ATPU/OMMT nanocomposites greatly depend on the amount of ATPU and OMMT. Results show that the addition of ATPU could increase the impact strength of UPR/ATPU composites, but the tensile strength, flexural strength and heat resistance of the materials are obviously decreased. When the weight ratio between UPR, ATPU and OMMT were 82：15：3, the impact strength and heat distortion-temperature of nanocomposite were greatly improved, meanwhile there was little change for other properties of the nanocomposites. The synergistic enhancement effects of ATPU and OMMT on the composites were observed. The structures and morphology of the composites were investigated by X-ray diffraction, scanning electron microscopy and transmission electron microscopy.

Stability analysis of an unsaturated soil slope considering rainfall infiltration based on the Green-Ampt model

Based on the principle of saturated infiltration and the Green-Ampt model,an unsaturated infiltration model for a soil slope surface was established for either constant moisture content,or depth-varying moisture content and the slope.Infiltration parameters in the partially saturated slope were revealed under sustained rainfall.Through analysis of the variation of initial moisture content in the slope,the ponding time,infiltration depth,and infiltration rate were deduced for an unsaturated soil slope subject to rainfall infiltration.There is no ponded water on the surface of the slope under sustained low-intensity rainfall.The results show that the infiltration parameters of an unsaturated slope are influenced by the initial moisture content and the wetting front saturation,the soil cohesion and rainfall intensity under sustained rainfall.More short-term slope failures can occur with the decrease of cohesion of the soil of the slope.The ponding time and infiltration depth differ considering constant or different initial moisture content respectively in the soil slope.Then,best-fit curves of the infiltration rate,ponding time,and infiltration depth to the wetting front saturation were obtained with constant or different initial moisture contents.And the slope failure time is roughly uniform when subject to a rainfall intensity I>5 mm/h.

Recent developments of generalized plasticity models for saturated and unsaturated soils

Soil undergoes both elastic and plastic deformations under different loading conditions. A relatively accurate constitutive model of soil behaviors should be capable of predicting the elastic and plastic deformations properly. Among a large number of elastoplastic constitutive models developed over the last several decades, constitutive models based on generalized plasticity have been successfully utilized in modeling the mechanical behavior of various soils. This paper attempts to present a review of the most recent developments of generalized plasticity models for geotechnical problems. After a brief review of generalized plasticity theories and constitutive models, limitations of the original Pastor-Zienkiewicz model in practical application are summarized. Afterwards, recent achievements in the generalized plasticity models for both saturated and unsaturated soils and their applicability are analyzed, and a general approach for modification of generalized plasticity models is highlighted.

Method of coupling 1-D unsaturated flow with 3-D saturated flow on large scale

A coupled unsaturated-saturated water flow numerical model was developed. The water flow in the unsaturated zone is considered the one-dimensional vertical flow, which changes in the horizontal direction according to the groundwater table and the atmospheric boundary conditions. The groundwater flow is treated as the three-dimensional water flow. The recharge flux to groundwater from soil water is considered the bottom flux for the numerical simulation in the unsaturated zone, and the upper flux for the groundwater simulation. It connects and unites the two separated water flow systems. The soil water equation is solved based on the assumed groundwater table.and the subsequent predicted recharge flux. Then, the groundwater equation is solved with the predicted recharge flux as the upper boundary condition. Iteration continues until the discrepancy between the assumed and calculated groundwater nodal heads have a certain accuracy. Illustrative examples with different water flow scenarios regar.ding the Dirichlet boundary condition, the Neumann boundary condition, the a.tmospheric boundary condition, and the source or sink term were calculated by the coupled model. The results are compared with those of other models, including Hydrus-lD, SWMS-2D, and FEFLOW, which demonstrate that the coupled model is effective and accurate and can significantly reduce the computational time for the large number of nodes in saturated-unsaturated water flow simulation.

Relationship of Resistivity with Water Content and Fissures of Unsaturated Expansive Soils

The development of fissures in expansive soils has a great effect on the stability of slope. Of the three phases of soils,the gas phase and solid phase are relatively insulated,so the average resistivity of soils can be calculated from the resistivity of the liquid phase. On this basis,the two-part model of resistivity changing with the water saturation of the expansive soil can be deduced. A 2-D resistance grid model is established based on simulating the resistance of ver-tically developed fissures. Variation in measured resistance of vertically developed fissures at different positions can be calculated from this model. Fissure development can be inversely determined from the variation in the measured resis-tance. Finally,the model is verified by an indoor resistivity test for remolded soil samples,indicating that the test result agrees well with that of the model established.

Preparation of Ternary Lanthanide Complexes with Unsaturated Acid and 1,10-Phenanthroline, and Their Anti-Inflammatory Action

Four ternary lanthanide complexes with unsaturated acid and 1,10-phenanthroline are prepared in methanol and characterized by elemental analysis, molar conductance, UV, IR, (()~1H) NMR and XPS. The results from this paper show that the complexes Ln(phen)(SA)_3·2H_2O or Ln(phen)(CA)_3·H_2O (Ln=Ce(Ⅲ), Sm(Ⅲ) and Eu(Ⅲ), (phen=1,10-)phenanthroline, SA=Sorbate and CA=Cinnamate) has better anti-inflammatory effect than cerium nitrate and their gremores are steadier than cerium nitrate gremor. And there is a kind of medicament which can replace the cerium nitrate gremor completely in treating burn.

Semi-analytical solutions to one-dimensional consolidation for unsaturated soils with semi-permeable drainage boundary

The semi-analytical solutions to Fredlund and Hasan＇s one-dimensional （1D） consolidation for unsaturated soils with a semi-permeable drainage boundary are pre- seated. Two variables are introduced to transform the two coupled governing equations of pore-water and pore-air pressures into an equivalent set of partial differential equations （PDFs）, which are easily solved by the Laplace transform method. Then, the pore-water pressure, pore-air pressure, and soil settlement are obtained in the Laplace domain. The Crump method is adopted to perform the inverse Laplace transform in order to obtain the semi-analytical solutions in the time domain. It is shown that the proposed solutions are more applicable to various types of boundary conditions and agree well with the existing solutions from the literature. Several numerical examples are provided to investigate the consolidation behavior of an unsaturated single-layer soil with single, double, mixed, and semi-permeable drainage boundaries. The changes in the pore-air and pore-water pres- sures and the soil settlement with the time factor at different values of the semi-permeable drainage boundary parameters are illustrated. In addition, parametric studies are con- ducted on the pore-air and pore-water pressures at different ratios （the air permeability coefficient to the water permeability coefficient） and depths.

A fully coupled thermo-hydro-mechanical model for unsaturated porous media

In examining potential host rocks for such purposes as the disposal of high-level radioactive wastes,it is important to understand the coupled thermo-hydro-mechanical（THM） behavior of a porous medium.A rigorous and fully unified coupled thermo-hydro-mechanical model for unsaturated porous media is required to simulate the complex coupling mechanisms involved.Based on modified Darcy＇s and Fourier＇s laws,equations of mechanical equilibrium,mass conservation and energy conservation are derived by introducing void ratio and volumetric liquid water content into the model.The newly derived model takes into account the effects of temperature on the dynamic viscosity of liquid water and void ratio,the influence of liquid flow on temperature gradient（thermo-osmosis）,the influence on mass and heat conservation equations,and the influence of heat flow on water pressure gradient and thermal convection.The new coupled THM constitutive model is constructed by a finite element program and is used to simulate the coupled behavior of a tunnel during excavation,ventilation and concrete lining stages.Oil and gas engineering,underground disposal of nuclear waste and tunnel engineering may be benefited from the development of the new model.