Novel Synthetic Method for the Vilsmeier-Haack Reagent and Green Routes to Acid Chlorides, Alkyl Formates, and Alkyl Chlorides

An environmentally benign and practical preparation method for the Vilsmeier-Haack reagent (VH) has been developed by using phthaloyl dichloride with DMF in toluene or 2-chlorotoluene. Phthalic anhydride as the byproduct was recovered in high yield by simple filtration. Some aromatic acids have been transformed into the corresponding acid chlorides in good yields by employing the isolated VH. Treatment of primary or secondary alcohols with VH gave alkyl formates or alkyl chlorides by depending on the reaction conditions.

Selective synthesis of carbon monoxide via formates in reverse water–gas shift reaction over alumina-supported gold catalyst

Thermal decomposition of formic acid on SiO2, CeO2 and γ-Al2O3 was studied as an elementary step of reverse water–gas shit reaction（RWGS） over supported Au catalysts. γ-Al2O3 showed the highest CO selectivity among the tested oxides in the decomposition of formic acid. Infrared spectroscopy showed the formation of four formate species on γ-Al2O3： three η~1-type and one μ~2-type species, and these formates decomposed to CO at 473 K or higher. Au-loaded γ-Al2O3 samples were prepared by a depositionprecipitation method and used as catalysts for RWGS. The supported Au catalyst gave CO with high selectivity over 99% from CO2 and H2, which is attributed to the formation of formates on Au and subsequent decomposition to CO on γ-Al2O3.

Episodic hydrothermal alteration on Middle Permian carbonate reservoirs and its geological significance in southwestern Sichuan Basin,SW China

To analyze the episodic alteration of Middle Permian carbonate reservoirs by complex hydrothermal fluid in southwestern Sichuan Basin,petrology,geochemistry,fluid inclusion and U-Pb dating researches are conducted.The fractures and vugs of Middle Permian Qixia–Maokou formations are filled with multi-stage medium-coarse saddle dolomites and associated hydrothermal minerals,which indicates that the early limestone/dolomite episodic alteration was caused by the large-scale,high-temperature,deep magnesium-rich brine along flowing channels such as basement faults or associated fractures under the tectonic compression and napping during the Indosinian.The time of magnesium-rich hydrothermal activity was from the Middle Triassic to the Late Triassic.The siliceous and calcite fillings were triggered by hydrothermal alteration in the Middle and Late Yanshanian Movement and Himalayan Movement.Hydrothermal dolomitization is controlled by fault,hydrothermal property,flowing channel and surrounding rock lithology,which occur as equilibrium effect of porosity and permeability.The thick massive grainstone/dolomites were mainly altered by modification such as hydrothermal dolomitization/recrystallization,brecciation and fracture-vugs filling.Early thin-medium packstones were mainly altered by dissolution and infilling of fracturing,bedding dolomitization,dissolution and associated mineral fillings.The dissolved vugs and fractures are the main reservoir space under hydrothermal conditions,and the connection of dissolved vugs and network fractures is favorable for forming high-quality dolomite reservoir.Hydrothermal dolomite reservoirs are developed within a range of 1 km near faults,with a thickness of 30–60 m.Hydrothermal dolomite reservoirs with local connected pore/vugs and fractures have exploration potential.

Early-diverging Titanosauriform(Dinosauria,Sauropoda)Teeth from the Lower Cretaceous Yixian Formation of Southeastern Inner Mongolia,Northeast China

Three eusauropod teeth(SDUST-V1064,PMOL-AD00176,PMOL-ADt0005)are reported from the Lower Cretaceous Yixian Formation of Ningcheng,southeastern Inner Mongolia,China.Two of them(SDUST-V1064,PMOL-AD00176)are assigned to early-diverging titanosauriforms in having slightly mesiodistal expansion at the base of the tooth crown,a slenderness index value>2.0 and<4.0,and D-shaped cross section.Furthermore,SDUST-V1064 and PMOL-AD00176 are referred as an Euhelopus-like titanosauriform on the basis of having a sub-circular boss on the lingual surface and an asymmetrical crown-root margin which slants apically,respectively.CT scan data of SDUST-V1064 reveals new dental information of early-diverging titanosauriforms,for example,the enamel on the labial side thicker than that on the lingual side,an enamel/dentine ratio of 0.26 and a boss present on the lingual side of the dentine of the crown.

Solid Bi_(2)O_(3)-derived nanostructured metallic bismuth with high formate selectivity for the electrocatalytic reduction of CO_(2)

CO_(2) electrochemical reduction(CO_(2)ER)is an important research area for carbon neutralization.However,available catalysts for CO_(2) reduction are still characterized by limited stability and activity.Recently,metallic bismuth(Bi)has emerged as a promising catalyst for CO_(2) ER.Herein,we report the solid cathode electroreduction of commercial micronized Bi2O3as a straightforward approach for the preparation of nanostructured Bi.At-1.1 V versus reversible hydrogen electrode in a KHCO3aqueous electrolyte,the resulting nanostructure Bi delivers a formate current density of~40 mA·cm^(-2) with a current efficiency of~86%,and the formate selectivity reaches97.6% at-0.78 V.Using nanosized Bi2O3as the precursor can further reduce the primary particle sizes of the resulting Bi,leading to a significantly increased formate selectivity at relatively low overpotentials.The high catalytic activity of nanostructured Bi is attributable to the ultrafine and interconnected Bi nanoparticles in the nanoporous structure,which exposes abundant active sites for CO_(2) electrocatalytic reduction.

Facies development and sedimentology of the Middle Miocene carbonates of the Raghama Formation, northeastern Saudi Arabia

Ragahama Formation comprises a siliciclastic continental deposits followed by marine carbonates, representing prograding alluvial fans from adjacent high hinterlands seaward into lagoons and fringing reef environments. The present work aimed to document the facies development and sedimentology of the Raghama carbonates exposed along the eastern coastal plain of the Red Sea, northwestern Saudi Arabia. Four stratigraphic sections were measured and sampled(D1–D4) and thin sections and major and trace element analyses were prepared and applied for petrographic and geochemical approaches. The carbonates were subdivided into three successive fore-reef, reef-core, and back-reef depositional facies. Sandy stromatolitic boundstone, microbial laminites, dolomitic ooidal grainstone, bioclastic coralline algal wackestone, sandy bioclastic wackestone, and coral boundstones were the reported microfacies types. Petrographic analysis reveals that the studied carbonates were affected by dissolution, dolomitization, and aggrading recrystallization, which affects both the original micrite matrix and grains or acts as fracture and veinlet filling leading to widespread vuggy and moldic porosity. No evidence of physical compaction, suggesting rapid lithification and recrystallization during early diagenesis and prior to substantial burial and intensive flushing by meteoric waters. Most of the original microstructure of corals were leached and destructed. This is indicated by the higher depletion in Sr and Ca levels and increase in Mg,Na, Fe, and Mn levels, especially in section D1, in comparison with the worldwide carbonates.

The Mass Assembly History for Galaxies with MaNGA

How galaxies assemble masses through their own star formation or interaction with the external environment is still an important topic in the field of galaxy formation and evolution.We use Value Added Catalogs with galaxy features that are spatially and temporally resolved from Sloan Digital Sky Survey Data Release 17 to investigate the mass growth histories of early-type galaxies(ETGs)and late-type galaxies(LTGs).We find that the mass growth of ETGs is earlier than that of LTGs for massive galaxies(M_(*)>10^(10)M_⊙),while low-mass(M_(*)≤10^(10)M_⊙)ETGs have statistically similar mass assembly histories as low-mass LTGs.The stellar metallicity of all massive galaxies shows a negative gradient and basically does not change with time.However,in low-mass galaxies,the stellar metallicity gradient of elliptical galaxies is negative,and the stellar metallicity gradient of lenticular and spiral galaxies evolves from positive to negative.ETGs are not all in a high-density environment,but exhibit mass dependence.As the tidal strength increases,the star formation rate of low-mass ETGs rapidly decreases.These results support a picture where massive galaxies exhibit inside-out quenching mode,while low-mass galaxies show outside-in quenching mode.Environmental effects play an important role in regulating the mass assembly histories of low-mass ETGs.

1.42-fold enhancement of formate selectivity by linker conversion on the Zn-based metal organic framework catalyst

Electro-reduction of carbon dioxide(ERCO_(2)) is considered an effective method to alleviate the greenhouse effect and produce value-added chemicals.Achieving the dominant selectivity of Zn-based catalysts for formate remains a challenge.In this article,the ZnIn-E_(12) catalyst is successfully prepared by solvent assisted ligand exchange(SALE) method to convert organic ligands,achieving a Faradaic efficiency of 72.28% for formate at-1.26 V vs.RHE(V_(RHE)),which is 1.42 times higher than the original catalyst.Evidence shows that the successful conversion of organic ligands can transform the catalyst from the original large size polyhedron to cross-linked network of particles with a diameter of about 30 nm.The increased specific surface area can expose more active sites and facilitate the electrocatalytic conversion of CO_(2) to formate.This work is expected to provide inspiration for the regulation of formate selectivity and catalyst size in Zn-based catalysts.

Arlenea delicata gen.et sp.nov.,a new ephedroid plant from the Early Cretaceous Crato Formation,Araripe Basin,Northeast Brazil

Ephedroid macrofossils have been widely documented in Cretaceous deposits,including numerous from the Lower Cretaceous Yixian Formation of NE China.However,few ephedroid macrofossils have been reported from South America.Herein,we describe a new plant of the family Ephedraceae,Arlenea delicata gen.et sp.nov.,from the Lower Cretaceous Crato Formation of the Araripe Basin,Northeast Brazil,based on the vegetative and reproductive structures.It has the typical morphological characteristics of ephedroid plants,including fertile reproductive branches,opposite phyllotaxy,terminal female cones,a sympodial branching system,longitudinally striated internodes,and swollen nodes.Our new finding is unusual in having inner chlamydosperms subtended by two pairs of bracts,reproductive units connected to branches through swollen receptacles and a smooth seed surface.This new ephedroid taxon from the Crato Formation increases our understanding of plant diversity of this group during the Early Cretaceous.Furthermore,the general morphology(fleshy bracts and enlarged receptacles)of this new fossil discovery indicates that seeds of this plant may have been dispersed by animals such as pterosaurs(mainly the Tapejaridae)and birds(Enantiornithes and Ornituromorpha).If true,this would explain the cosmopolitan distribution of Ephedraceae in the Lower Cretaceous.

Pedestrian lane formation with following–overtaking model and measurement of system order

Pedestrian self-organizing movement plays a significant role in evacuation studies and architectural design.Lane formation,a typical self-organizing phenomenon,helps pedestrian system to become more orderly,the majority of following behavior model and overtaking behavior model are imprecise and unrealistic compared with pedestrian movement in the real world.In this study,a pedestrian dynamic model considering detailed modelling of the following behavior and overtaking behavior is constructed,and a method of measuring the lane formation and pedestrian system order based on information entropy is proposed.Simulation and analysis demonstrate that the following and avoidance behaviors are important factors of lane formation.A high tendency of following results in good lane formation.Both non-selective following behavior and aggressive overtaking behavior cause the system order to decrease.The most orderly following strategy for a pedestrian is to overtake the former pedestrian whose speed is lower than approximately 70%of his own.The influence of the obstacle layout on pedestrian lane and egress efficiency is also studied with this model.The presence of a small obstacle does not obstruct the walking of pedestrians;in contrast,it may help to improve the egress efficiency by guiding the pedestrian flow and mitigating the reduction of pedestrian system orderliness.

Sema3A secreted by sensory nerve induces bone formation under mechanical loads

Bone formation and deposition are initiated by sensory nerve infiltration in adaptive bone remodeling. Here, we focused on the role of Semaphorin 3A(Sema3A), expressed by sensory nerves, in mechanical loads-induced bone formation and nerve withdrawal using orthodontic tooth movement(OTM) model. Firstly, bone formation was activated after the 3rd day of OTM,coinciding with a decrease in sensory nerves and an increase in pain threshold. Sema3A, rather than nerve growth factor(NGF),highly expressed in both trigeminal ganglion and the axons of periodontal ligament following the 3rd day of OTM. Moreover, in vitro mechanical loads upregulated Sema3A in neurons instead of in human periodontal ligament cells(hPDLCs) within 24 hours.Furthermore, exogenous Sema3A restored the suppressed alveolar bone formation and the osteogenic differentiation of hPDLCs induced by mechanical overload. Mechanistically, Sema3A prevented overstretching of F-actin induced by mechanical overload through ROCK2 pathway, maintaining mitochondrial dynamics as mitochondrial fusion. Therefore, Sema3A exhibits dual therapeutic effects in mechanical loads-induced bone formation, both as a pain-sensitive analgesic and a positive regulator for bone formation.

Diagenetic evolution and reservoir quality of the Oligocene sandstones in the Baiyun Sag, Pearl River Mouth Basin, South China Sea

The Oligocene Zhuhai sandstones are significant reservoirs for hydrocarbons in the Baiyun Sag, South China Sea.For effective appraisal, exploration and exploitation of such a deep-water hydrocarbon sandstone, samples of five wells from depths of 850 m to 3 000 m were studied. A series of comprehensive petrographic and geochemical analyses were performed to unravel the diagenetic features and their impact on the reservoir quality.Petrographically, the sandstones are dominated by feldspathic litharenites and lithic arenites with fine to medium grain sizes and moderate to good sorting. The reservoir quality varies greatly with a range of porosity from 0.2% to 36.1% and permeability from 0.016 ×10~(–3) μm~2 to 4 301 ×10~(–3) μm~2, which is attributed to complex diagenetic evolution related to sedimentary facies;these include compaction, cementation of calcite, dolomite, siderite and framboidal pyrite in eogenetic stage;further compaction, feldspar dissolution, precipitation of ferrocalcite and ankerite, quartz cements, formation of kaolinite and its illitization, precipitation of albite and nodular pyrite, as well as hydrocarbon charge in mesogenetic stage. The dissolution of feldspar and illitization of kaolinite provide internal sources for the precipitation of quartz cement, while carbonate cements are derived from external sources related to interbedded mudstones and deep fluid. Compaction is the predominant factor in reducing the total porosity, followed by carbonate cementation that leads to strong heterogeneity. Feldspar dissolution and concomitant quartz and clay cementation barely changes the porosity but significantly reduces the permeability.The high-quality reservoirs can be concluded as medium-grained sandstones lying in the central parts of thick underwater distributary channel sandbodies(>2 m) with a high content of detrital quartz but low cement.

Mechanical Modeling and Analysis of Stability Deterioration of Production Well During Marine Hydrate Depressurization Production

Different from oil and gas production,hydrate reservoirs are shallow and unconsolidated,whose mechanical properties deteriorate with hydrate decomposition.Therefore,the formations will undergo significant subsidence during depressurization,which will destroy the original force state of the production well.However,existing research on the stability of oil and gas production wells assumes the formation to be stable,and lacks consideration of the force exerted on the hydrate production well by formation subsidence caused by hydrate decomposition during production.To fill this gap,this paper proposes an analytical method for the dynamic evolution of the stability of hydrate production well considering the effects of hydrate decomposition.Based on the mechanical model of the production well,the basis for stability analysis has been proposed.A multi-field coupling model of the force state of the production well considering the effect of hydrate decomposition and formation subsidence is established,and a solver is developed.The analytical approach is verified by its good agreement with the results from the numerical method.A case study found that the decomposition of hydrate will increase the pulling-down force and reduce the supporting force,which is the main reason for the stability deterioration.The higher the initial hydrate saturation,the larger the reservoir thickness,and the lower the production pressure,the worse the stability or even instability.This work can provide a theoretical reference for the stability maintaining of the production well.

Provenance and depositional setting of the Late MiocenePleistocene clastic sediments in the eastern Arabian Peninsula and western Iraq using rare earth elements geochemistry

The sandstones of the Late miocene–Pliocene Dibdibba Formation in the Najaf–Karbala Plateau and Basra were examined to determine their source rocks and origin. The rare earth elements(REE) and trace elements(Sc, Co, V, and Th) concentrations in these sandstones revealed that they likely derived from a single source. The steep light rare earth elements(LREE) and flat, heavy rare earth element(HREE) patterns, negative Eu anomaly, and high ΣREE contents in sandstones suggest its derivation from a suggests that a passive continental margin environment and originated from felsic source rocks. The average concentration of ΣREE is 93.5 ppm, which is lower than that of the average crustal compositions like Upper Continental Crust and Post Archean Australian Shale. The higher proportion of LREE compared to HREE implies that these sandstones were recycled and derived from a distal source. The Th/Co, Th/Sc, La/Sc, La/Co, Eu/Eu*and(La/Lu)cn elemental ratios indicated that these Late Miocene–Pliocene sandstones were derived from felsic rocks located in the marginal region of the Arabian Shield.

Laser-induced plasma formation in water with up to 400 mJ double-pulse LIBS

Double-pulse LIBS is a promising technique for deep-sea applications.LIBS measurements in shallow water with up to 400 mJ each pulse were done to select laser parameters which promote optimized spectral line emission from plasma even at elevated pressures,where line broadening until loss of most of the spectral information can occur.Optical emission spectroscopy,using a Czerny-Turner spectrometer,has been applied to investigate the dependence of the emitted radiation on laser parameters and hydrostatic pressure.It has been found,that higher laser pulse energies,especially with short pulse delay as required in high water pressure,can also have an adverse effect on the measured spectrum.

Brent vs.West Texas Intermediate in the US petro derivatives price formation

In this paper,we apply the spatial panel model to explore the relationship between the dynamic of two types of crude oil prices(WTI and Brent crude oil)and their refined products over time.Considering the turbulent months of 2011,when Cushing Oklahoma had reached capacity and the crude oil export ban removal in 2015 as breakpoints,we apply this method both in the full sample and the three resultant regimes.First,results suggest our results show that both WTI and Brent display very similar behaviour with the refined products.Second,when attending to each regime,results derived from the first and third regimes are quite similar to the full sample results.Therefore,during the second regime,Brent crude oil became the benchmark in the petrol market,and it influenced the distillate products.Furthermore,our model can let us determine the price-setters and price-followers in the price formation mechanism through refined products.These results possess important considerations to policymakers and the market participants and the price formation.

Simulation of liquid cone formation on the tip apex of indium field emission electric propulsion thrusters

Field emission electric propulsion(FEEP) thrusters possess excellent characteristics, such as high specific impulse, low power requirements, compact size and precise pointing capabilities,making them ideal propulsion devices for micro-nano satellites. However, the detection of certain aspects, such as the evolution process of the liquid cone and the physical quantities at the cone apex, proves challenging due to the minute size of the needle tip and the vacuum environment in which they operate. Consequently, this paper introduces a computational fluid dynamics(CFD) model to gain insight into the formation process of the liquid cone on the tip apex of indium FEEP. The CFD model is based on electrohydrodynamic(EHD) equations and the volume of fluid(VOF) method. The entire cone formation process can be divided into three stages, and the time-dependent characteristics of the physical quantities at the cone apex are investigated. The influences of film thickness, apex radius size and applied voltage are compared.The results indicate a gradual increase in the values of electrostatic stress and surface tension stress at the cone apex over an initial period, followed by a rapid escalation within a short duration.Apex configurations featuring a small radius, thick film and high voltage exhibit a propensity for liquid cone formation, and the cone growth time decreases as the film thickness increases.Moreover, some unstable behavior is observed during the cone formation process.

Geometry and formation mechanism of tension gashes and their implication on the hydrocarbon accumulation in the deep-seated strata of sedimentary basin:A case from Shunnan area of Tarim Basin

With the theoretical and technological developments related to cratonic strike-slip faults,the Shuntuoguole Low Uplift in the Tarim Basin has attracted considerable attention recently.Affected by multi-stage tectonic movements,the strike-slip faults have controlled the distribution of hydrocarbon resources owing to the special fault characteristics and fault-related structures.In contrast,the kinematics and formation mechanism of strike-slip faults in buried sedimentary basins are difficult to investigate,limiting the discussion of these faults and hydrocarbon accumulation.In this study,we identified the characteristics of massive sigmoidal tension gashes(STGs)that formed in the Shunnan area of the Tarim Basin.High-resolution three-dimensional seismic data and attribute analyses were used to investigate their geometric and kinematic characteristics.Then,the stress state of each point of the STGs was calculated using seismic curvature attributes.Finally,the formation mechanism of the STGs and their roles in controlling hydrocarbon migration and accumulation were discussed.The results suggest that:(1)the STGs developed in the Shunnan area have a wide distribution,with a tensile fault arranged in an enéchelon pattern,showing an S-shaped bending.These STGs formed in multiple stages,and differential rotation occurred along the direction of strike-slip stress during formation.(2)Near the principal displacement zone of the strike-slip faults,the stress value of the STGs was higher,gradually decreasing at both ends.The shallow layer deformation was greater than the deep layer deformation.(3)STGs are critical for connecting source rocks,migrating oil and gas,sealing horizontally,and developing efficient reservoirs.This study not only provides seismic evidence for the formation and evolution of super large STGs,but also provides certain guidance for oil and gas exploration in this area.

Numerical Simulation on Production Trials by Using Depressurization for Typical Marine Hydrate Reservoirs:Well Type and Formation Dip

Natural gas hydrate has huge reserves and is widely distributed in marine environment.Its commercial development is of great significance for alleviating the contradiction between energy supply and demand.As an efficient research method,numerical simulation can provide valuable insights for the design and optimization of hydrate development.However,most of the current production models simplify the reservoir as a two-dimensional(2D)horizontal layered model,often ignoring the impact of formation dip angle.To improve the accuracy of production prediction and provide theoretical support for the optimization of production well design,two three-dimensional(3D)geological models with different dip angles based on the geological data from two typical sites are constructed.The vertical well,horizontal well and multilateral wells are deployed in these reservoirs with different permeabilities to perform production trial,and the sensitivity analysis of dip angles is also carried out.The short-term production behaviors in high and low permeability reservoirs with different dip angles are exhibited.The simulation results show that 1)the gas and water production behaviors for different well types in the two typical reservoirs show obviously different variation laws when the short-term depressurization is conducted in the inclined formation;2)the inclined formation will reduce the gas production and increase the water extraction,and the phenomena becomes pronounced as the dip angle increases,particularly in the low-permeability reservoirs;3)and the impact of formation dip on hydrate recovery does not change significantly with the variation of well type.

The occurrence characteristics of oil in shales matrix from organic geochemical screening data and pore structure properties:An experimental study Author links open overlay panel

The occurrence characteristics of shale oil are of great significance to the movability of shale oil.In this study,the occurrence characteristics of oil in the shale matrix at Funing Formation shale in Subei Basin were quantitatively evaluated by organic geochemistry and microscopic pore structure characterization experiments.The Multiple Isothermal Stages Pyrolysis(MIS)experiment results show that the content of total oil,adsorbed oil,and free oil in the shales are 3.15-11.25 mg/g,1.41-4.95 mg/g,and 1.74-6.51 mg/g,respectively.among which the silicon-rich shale has the best oil-bearing.The relative content of free oil shows an increasing trend in pores with pore diameters greater than 3 nm.When the relative content of free oil reaches 100%,the pore size of silicon-rich shale is about 200 nm,while that of calcium-rich shale,clay-rich shale,and siliceous mixed shale is about 10 nm.The occurrence law of adsorbed oil is opposite to that of free oil,which indicates that shale oil will occur in the pores and fractures in a free state in a more extensive pore size range(>200 nm).This study also enables us to further understand the occurrence characteristics of shale oil under the interaction of occurrence state and occurrence space.