Selective Reduction of α,β-Unsaturated Amides with NaBH_4/BiCl_3 System

?β-Unsaturated amides with various substitution pattems at the carbon-carbon double And and nitrogen atom can be reduced to the corresponding saturated amides with high selectivity and yields with NaBH4/BiCl3 system.

Synthesis of （2E）－α，β－Unsaturated Amides Catalyzed by Micro Palladium Under Solid－Liquid Phase－Transfer Conditions

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A FACILE SYNTHESIS OF 2-AND 2,4-UNSATURATED AMIDES

A convenient method for preparing unsaturated amides via telluro- nium salts employing solid potassium carbonate as a base with high stereo- selectivity in excellent yields has been developed.

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.

Removal of Dye Using Lignin-Based Biochar/Poly(ester amide urethane)Nanocomposites from Contaminated Wastewater

The pursuit of incorporating eco-friendly reinforcing agents in polymer composites has accentuated the exploration of various natural biomass-derived materials.The burgeoning environmental crisis spurred by the discharge of synthetic dyes into wastewater has catalyzed the search for effective and sustainable treatment technologies.Among the various sorbent materials explored,biochar,being renewable,has gained prominence due to its excellent adsorption properties and environmental sustainability.It has also emerged as a focal point for its potential to replace other conventional reinforcing agents,viz.,fumed silica,aluminum oxide,treated clays,etc.This study introduces a novel class of polymer nanocomposites comprising of lignin-based biochar particles and poly(ester amide urethane)matrix via a feasible method.The structural evaluation of these nanocomposites was accomplished using Fourier-transform infrared spectroscopy,X-ray photoelectron spectroscopy,and powder X-ray diffraction.The polymer nanocomposites exhibited superior mechanical properties with an increment in tensile strength factor by 45%in comparison to its pristine matrix,along with an excellent toughness value of 90.22 MJm^(−3)at a low loading amount of only 1 wt%.The composites showed excellent improvement in thermal properties with a sharp rise in the glass transition temperature(Tg)value from−28.15℃to 84℃,while also championing sustainability through inherent biodegradability attributes.Beyond their structural prowess,these polymer nanocomposites demonstrated excellent potential as adsorbents,displaying efficient removal of malachite green and tartrazine dyes from aqueous systems with a removal efficiency of 87.25%and 73.98%,respectively.The kinetics study revealed the pseudo second order model to be the precision tool to assess the dye removal study.Complementing this,the Langmuir adsorption isotherm provided a framework to assess the sorption features of the polymer nanocomposites.Overall,these renewable biochar integrated polymer matrices boast remarkable recovery capabilities up to seven cycles of usage with an excellent dye recovery percentage of 95.21%for the last cycle,thereby defining sustainability as well as economic feasibility.

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 ...

大位阻氨基酸Fmoc-Arg(Pbf)-OH与Rink Amide-AM树脂的高效缩合

采用集自动搅拌、过滤、鼓泡等多重功能于一体的自制多肽固相合成反应器,以对称酸酐法、活化酯法、2,6-二氯苯甲酰氯(DCB)法研究了大位阻氨基酸Fmoc-Arg(Pbf)-OH与Rink Amide-AM树脂的连接反应工艺。探讨了催化体系、溶剂体系、反应时间、反应物配比以及搅拌方式对合成Fmoc-Arg(Pbf)-Rink Amide-AM树脂反应的影响。结果表明,采用活化酯法(DIC/HOBt/DMAP)时连接率最高,最佳反应条件为:在采用N2辅助磁力拌系统,以体积比为1∶1的DMA/DCM为反应溶剂,氨基酸与树脂物质的量的比为3∶1,反应时间为3 h时,连接率高达93%。

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.

天然产物Trichodermamide类似物的合成

以8a-甲氧基-4,4a,5,8-四氢-1,2-苯并口恶嗪-3-羧酸乙酯(1a)为起始原料,经NaOH醇溶液和酸处理,在4-pyrrolidinopyridine和碳化双(环己基亚胺)(DCC)的存在下与3-氨基-7,8-二甲氧基香豆素(2)进行了酰胺化反应,合成了天然产物Trichodermamides的类似物T-1,总收率为61.6%,T-1通过了1HNMR,13CNMR,IR和元素分析等光谱学的结构表征;同时水解反应研究发现,含苯并口恶嗪双环结构的化合物1a可水解脱去酯基,而口恶嗪双环8a位上连有两个O的缩酮类似结构可稳定地保留。

Research Status of Amide Herbicides and Their Safeners

The widespread use of chemical herbicides especially amide herbicides has promoted the innovation of chemical weeding in farmland, but amide herbicides have brought invisible chemical injuries to crops in addition to weeding. Herbi-cidesafeners should be applied at the same time with herbicides to ensure herbi- cides will not injure crops while controlling weeds. The research and application of safeners is of great significance to resolving or alleviating the negative effects of herbicides on crop growth. The overview, mechanism, applied research progress and existing problems of amide herbicides and their safenars are summarized.

In situ Detection of Amide A Bands of Proteins in Water by Raman Ratio Spectrum

The amide A band of protein is sensitive to the hydrogen bands of amide groups of proteins. However, it is hard to distinguish the amide A band of aqueous protein in situ directly, since it overlaps with O-H stretching vibration of water. In this work, we presented a new analytical method of Raman ratio spectrum, which can extract the amide A band of proteins in water. To obtain the Raman ratio spectrum, the Raman spectrum of aqueous protein was divided by that of pure water. A mathematical simulation was employed to examine whether Raman ratio spectrum is effective. Two kinds of protein, lysozyme and （^-chymotrypsin were employed. The amide A bands of them in water were extracted from Raman ratio spectra. Additionally, the process of thermal denaturation of lysozyme was detected from Raman ratio spectrum. These results demonstrated the Raman ratio spectra could be employed to study the amide A modes of proteins in water.

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.

L-theanine: A potential multifaceted natural bioactive amide as health supplement

Natural bioactive compounds from plants are of great importance in modern therapeutics,which are used to prepare antibiotics, growth supplements or some other therapeutics. Ltheanine is such a bioactive amide amino acid presented in different plants and fungi,especially in tea. Theanine has influential effects on lifestyle associated diseases, such as diabetes, cardiovascular disorders, hypertension, stress relief, tumor suppression,menstruation and liver injury. This amino acid can maintain normal sleep and improve memory function and nullify effect of the neurotoxins. The rate of bioavailability and its medium of ingestion in the body is one of the great concerns for its additional antioxidant properties. Pharmacokinetics of the bioactive compound and its mode of action are described herewith. The biosynthesis and industrial synthesis are also reviewed to promote accelerated production of this bioactive compound in the pharmaceutical industries.