CO_(2)-assisted oxidation dehydrogenation of light alkanes over metal-based heterogeneous catalysts

Light olefins are important platform feedstocks in the petrochemical industry,and the ongoing global economic development has driven sustained growth in demand for these compounds.The dehydrogenation of alkanes,derived from shale gas,serves as an alternative olefins production route.Concurrently,the target of realizing carbon neutrality promotes the comprehensive utilization of greenhouse gas.The integrated process of light alkanes dehydrogenation and carbon dioxide reduction(CO_(2)-ODH)can produce light olefins and realize resource utilization of CO_(2),which has gained wide popularity.With the introduction of CO_(2),coke deposition and metal reduction encountered in alkanes dehydrogenation reactions can be effectively suppressed.CO_(2)-assisted alkanes dehydrogenation can also reduce the risk of potential explosion hazard associated with O_(2)-oxidative dehydrogenation reactions.Recent investigations into various metal-based catalysts including mono-and bi-metallic alloys and oxides have displayed promising performances due to their unique properties.This paper provides the comprehensive review and critical analysis of advancements in the CO_(2)-assisted oxidative dehydrogenation of light alkanes(C2-C4)on metal-based catalysts developed in recent years.Moreover,it offers a comparative summary of the structural properties,catalytic activities,and reaction mechanisms over various active sites,providing valuable insights for the future design of dehydrogenation catalysts.

Controlling Reactivity of Palladium Amides for Selective Carbonylation towards Urea and Oxamide Derivatives

Carbonylation reactions,crucial for carbonyl group incorporation,struggle with the inherent complexity of achieving selective mono-or double-carbonylation on single substrates,often due to competing reaction pathways.Herein,our study introduces a strategy employing palladium amides,harnessing their unique reactivity control,to direct the selective carbonylation of amines for the targeted synthesis of urea and oxamide derivatives.The palladium amide structure was elucidated using single-crystal X-ray diffraction.Controlled experiments and cyclic voltammetry studies further elucidate that the oxidation of palladium amide or its insertion into a carbonyl group diverges into distinct pathways.By employing sodium percarbonate as an eco-friendly oxidant and base,we have successfully constructed a switchable carbonylation system co-catalyzed by palladium and iodide under room temperature.The utilizing strategy in this study not only facilitates effective control over reaction selectivity but also mitigates the risk of explosions,a critical safety concern in traditional carbonylation methods.

Mechanism study on the influence of surface properties on the synthesis of dimethyl carbonate from CO_(2)and methanol over ceria catalysts

The direct synthesis of dimethyl carbonate(DMC)from CO_(2)and methanol has attracted much attention as an environmentally benign and alternative route for conventional routes.Herein,a series of cerium oxide catalysts with various textural features and surface properties were prepared by the one-pot synthesis method for the direct DMC synthesis from CO_(2)and methanol,and the structure-performance relationship was investigated in detail.Characterization results revealed that both of surface acid-base properties and the oxygen vacancies contents decreased with the rising crystallinity at increasingly higher calcination temperature accompanied by an unexpectedly volcano-shaped trend of DMC yield observed on the catalysts.In situ diffuse reflectance infrared Fourier transform spectroscopy(DRIFTS)studies indicated that the adsorption rate of methanol is slower than that of CO_(2)and the methanol activation state largely influences the formation of key intermediate.Although the enhanced surface acidity-basicity and oxygen vacancies brought by low-temperature calcination could facilitate the activation of CO_(2),the presence of excess strongly basic sites on low-crystallinity sample was detrimental to DMC synthesis due to the preferred formation of unreactive mono/polydentate carbonates as well as the further impediment of methanol activation.Moreover,with the use of 2-cyanopyridine as a dehydration reagent,the DMC synthesis was found to be both influenced by the promotion from the rapid in situ removal of water and the inhibition from the competitive adsorption of hydration products on the same active sites.

Performance of Lateral 4H-SiC Photoconductive Semiconductor Switches by Extrinsic Backside Trigger

Photoconductive semiconductor switch(PCSS)can be applied in pulsed high power systems and microwave techniques.However,reducing the damage and increasing the lifetime of silicon carbide(SiC)PCSS are still faced severe challenges.In this study,PCSSs with various structures were prepared on 4-inch diameter,500μm thick high-purity semi-insulating 4H-SiC substrates and their on-state resistance and damage mechanisms were investigated.It was found that the PCSS of an Au/TiW/Ni electrode system annealed at 950℃had a minimum on-state resistance of 6.0Ωat 1 kV bias voltage with a 532 nm and 170 mJ pulsed laser by backside illumination single trigger.The backside illumination single trigger could reduce on-state resistance and alleviate the damage of PCSS compared to the frontside trigger when the diameter of the laser spot was larger than the channel length of PCSS.For the 200 s trigger test by a 10 Hz laser,the black branch-like ablation on Au/TiW/Ni PCSS was mainly caused by thermal stress owing to hot carriers.Replacing metal Ni with boron gallium co-doped zinc oxide(BGZO)thin films annealed at 400℃,black branch-like ablation was alleviated while concentric arc damage was obvious at the anode.The major causes of concentric arc are both pulsed laser diffraction and thermal effect.

A Hybrid Dung Beetle Optimization Algorithm with Simulated Annealing for the Numerical Modeling of Asymmetric Wave Equations

In the generalized continuum mechanics(GCM)theory framework,asymmetric wave equations encompass the characteristic scale parameters of the medium,accounting for microstructure interactions.This study integrates two theoretical branches of the GCM,the modified couple stress theory(M-CST)and the one-parameter second-strain-gradient theory,to form a novel asymmetric wave equation in a unified framework.Numerical modeling of the asymmetric wave equation in a unified framework accurately describes subsurface structures with vital implications for subsequent seismic wave inversion and imaging endeavors.However,employing finite-difference(FD)methods for numerical modeling may introduce numerical dispersion,adversely affecting the accuracy of numerical modeling.The design of an optimal FD operator is crucial for enhancing the accuracy of numerical modeling and emphasizing the scale effects.Therefore,this study devises a hybrid scheme called the dung beetle optimization(DBO)algorithm with a simulated annealing(SA)algorithm,denoted as the SA-based hybrid DBO(SDBO)algorithm.An FD operator optimization method under the SDBO algorithm was developed and applied to the numerical modeling of asymmetric wave equations in a unified framework.Integrating the DBO and SA algorithms mitigates the risk of convergence to a local extreme.The numerical dispersion outcomes underscore that the proposed SDBO algorithm yields FD operators with precision errors constrained to 0.5‱while encompassing a broader spectrum coverage.This result confirms the efficacy of the SDBO algorithm.Ultimately,the numerical modeling results demonstrate that the new FD method based on the SDBO algorithm effectively suppresses numerical dispersion and enhances the accuracy of elastic wave numerical modeling,thereby accentuating scale effects.This result is significant for extracting wavefield perturbations induced by complex microstructures in the medium and the analysis of scale effects.

The relationship between the high-frequency performance of supercapacitors and the type of doped nitrogen in the carbon electrode

Nitrogen doping has been widely used to improve the performance of carbon electrodes in supercapacitors,particularly in terms of their high-frequency response.However,the charge storage and electrolyte ion response mechanisms of different nitrogen dopants at high frequencies are still unclear.In this study,melamine foam carbons with different configurations of surfacedoped N were formed by gradient carbonization,and the effects of the configurations on the high-frequency response behavior of the supercapacitors were analyzed.Using a combination of experiments and first-principle calculations,we found that pyrrolic N,characterized by a higher adsorption energy,increases the charge storage capacity of the electrode at high frequencies.On the other hand,graphitic N,with a lower adsorption energy,increases the speed of ion response.We propose the use of adsorption energy as a practical descriptor for electrode/electrolyte design in high-frequency applications,offering a more universal approach for improving the performance of N-doped carbon materials in supercapacitors.

The application of metal-organic frameworks and their derivatives for lithium-ion capacitors

There is an urgent need for lithium-ion capacitors(LICs)that have both high energy and high power densities to meet the continuously growing energy storage demands.LICs effectively balance the high energy density of traditional rechargeable batteries with the superior power density and long life of supercapacitors(SCs).Nevertheless,the development of LICs is still hampered by limited kinetic processes and capacity mismatch between the cathode and anode.Metal-organic frameworks(MOFs)and their derivatives have received significant attention because of their extensive specific surface area,different pore structures and topologies,and customizable functional sites,making them compelling candidate materials for achieving high-performance LICs.MOF-derived carbons,known for their exceptional electronic conductivity and large surface area,provide improved charge storage and rapid ion transport.MOF-derived transition metal oxides contribute to high specific capacities and improved electrochemical stability.Additionally,MOF-derived metal compounds/carbons provide combined effects that increase both the capacitive and Faradaic reactions,leading to a superior overall performance.The review begins with an overview of the fundamental principles of LICs,followed by an exploration of synthesis strategies and ligand selection for MOF-based composite materials.It then analyzes the advantages of original MOFs and their derived materials,such as carbon materials and metal compounds,in enhancing LIC performance.Finally,the review discusses the major challenges faced by MOFs and their derivatives in LIC applications and offers future research directions and recommendations.

The Late Miocene‘ovibovin’bovids in Eurasia

During the Late Miocene,numerous medium to large-sized herbivores,that resemble the living Ovibos in skeletal morphology,dispersed throughout the Holarctic realm and comprised eleven genera:Lantiantragus,Shaanxispira,Tsaidamotherium,Criotherium,Mesembriacerus,Hezhengia,Urmiatherium,Parurmiatherium,Plesiaddax,Sinotragus,and Prosinotragus.These genera are primarily found in eastern Asia,in which nine genera are found in northern China,as well as in countries in eastern Europe and western Asia.They are distinguished by unique characteristics,including a perpendicular braincase,specialized horn cores,and a robust basioccipital.Previous studies have often classified these‘ovibovin’bovids as part of the conventional subfamily/tribe Ovibovinae/Ovibovini,along with extant Ovibos.Nevertheless,an increasing number of studies do not support the monophyly of the subfamily/tribe Ovibovinae/Ovibovini,nor is a close relationship likely between these Late Miocene‘ovibovin’bovids and extant Ovibos.Among the eleven genera of‘ovibovin’bovids,Plesiaddax,Hezhengia,and Urmiatherium are often considered to have a very close relationship and conventionally form the tribe Urmiatheriini.However,previous phylogenetic analyses do not support the monophyly of Urmiatheriini.This paper presents a summary of the transmutation of the terms Ovibovidae/Ovibovinae/Ovibovini/Ovibovina,the temporal and spatial distribution of the Late Miocene‘ovibovin’bovids in Eurasia,the principal characteristics of these taxa,and the previous phylogenetic analyses.

Regulating crystal phase of TiO_(2) to enhance catalytic activity of Ni/TiO_(2) for solar-driven dry reforming of methane

Ni/TiO_(2) catalyst is widely employed for photo-driven DRM reaction while the influence of crystal structure of TiO_(2) remains unclear.In this work,the rutile/anatase ratio in supports was successfully controlled by varying the calcination temperature of anatase-TiO_(2).Structural characterizations revealed that a distinct TiO_(x) coating on the Ni nanoparticles(NPs)was evident for Ni/TiO_(2)-700 catalyst due to strong metal-support interaction.It is observed that the TiOx overlayer gradually disappeared as the ratio of rutile/anatase increased,thereby enhancing the exposure of Ni active sites.The exposed Ni sites enhanced visible light absorption and boosted the dissociation capability of CH4,which led to the much elevated catalytic activity for Ni/TiO_(2)-950 in which rutile dominated.Therefore,the catalytic activity of solar-driven DRM reaction was significantly influenced by the rutile/anatase ratio.Ni/TiO_(2)-950,characterized by a predominant rutile phase,exhibited the highest DRM reactivity,with remarkable H_(2) and CO production rates reaching as high as 87.4 and 220.2 mmol/(g·h),respectively.These rates were approximately 257 and 130 times higher,respectively,compared to those obtained on Ni/TiO_(2)-700 with anatase.This study suggests that the optimization of crystal structure of TiO_(2) support can effectively enhance the performance of photothermal DRM reaction.

Rational Synthesis of Crystalline Covalent Triazine Framework with Methylthio Pendant Arms for Efficient Mercury(Ⅱ)Adsorption

The interest in curtailing environmental pollution issues through physical separation processes has inspired an extensive search for novel nanoporous materials with exceptional adsorption capabilities.Covalent triazine frameworks(CTFs),emerged as a class of crystalline covalent organic frameworks(COFs),have been widely examined for various separation applications,owing to their large porosity,high stability,and rich nitrogen(N)doping.The development of CTFs for efficient adsorption of mercury(Ⅱ)(Hg^(2+))is of great importance for the field,whereas it is rarely attempted,on account of limited synthetic strategies and unknown structural-property relations of conventional CTFs derived from ionothermal approaches.Herein,we report rational synthesis of a crystalline CTF with methylthio pendant arms for efficient removal of Hg^(2+)with an exceptional capacity of 751 mg·g^(-1),ranking at the top among previously-reported adsorbents.This work may open up new possibility in the synthesis of COFs for various separations.

Controllable synthesis of CuAlO_(2) via solid-phase method and its catalytic performance for methanol steam reforming to hydrogen

This study explores the controllable synthesis of CuAlO_(2) using copper hydroxide and pseudo-boehmite powders as raw materials via a simple solid-phase ball milling method,along with its catalytic performance investigation in methanol steam reforming(MSR).Various catalysts were prepared under different conditions,such as calcination temperature,calcination atmosphere,and heating rate.Characterization techniques including BET,XRD,XPS,SEM and H2-TPR were employed to analyze the samples.The results revealed significant effects of calcination temperature on the phase compositions,specific surface area,reduction performance,and surface properties of the CA-T catalysts.Based on the findings,a synthesis route of CuAlO_(2) via the solid-phase method was proposed,highlighting the importance of high calcination temperature,nitrogen atmosphere,and low heating rate for CuAlO_(2) formation.Catalytic evaluation data demonstrated that CuAlO_(2) could catalyze MSR without pre-reduction,with the catalytic performance of CA-T catalysts being notably influenced by calcination temperature.Among the prepared catalysts,the CA-1100 catalyst exhibited the highest catalytic activity and stability.The findings of this study might be useful for the further study of the catalytic material for sustained release catalysis,including the synthesis of catalytic materials and the regulation of sustained release catalytic performance.

Engineering the coordination structure of Cu for enhanced photocatalytic production of C_(1) chemicals from glucose

Photocatalytic decomposition of sugars is a promising way of providing H_(2),CO,and HCOOH as sus-tainable energy vectors.However,the production of C_(1) chemicals requires the cleavage of robust C−C bonds in sugars with concurrent production of H_(2),which remains challenging.Here,the photo-catalytic activity for glucose decomposition to HCOOH,CO(C_(1) chemicals),and H_(2) on Cu/TiO_(2)was enhanced by nitrogen doping.Owing to nitrogen doping,atomically dispersed and stable Cu sites resistant to light irradiation are formed on Cu/TiO_(2).The electronic interaction between Cu and nitrogen ions originates valence band structure and defect levels composed of N 2p orbit,distinct from undoped Cu/TiO_(2).Therefore,the lifetime of charge carriers is prolonged,resulting in the pro-duction of C_(1) chemicals and H_(2) with productivities 1.7 and 2.1 folds that of Cu/TiO_(2).This work pro-vides a strategy to design coordinatively stable Cu ions for photocatalytic biomass conversion.

Physicochemical composition and climate response of surface sediments at different altitudes in Motuo on the southern slope of the Himalayas

Background,aim,and scope Certain physicochemical indexes of topsoil are closely related to climatic factors including temperature,and precipitation.Understanding the relationship between modern topsoil properties and climatic factors is essential for quantitative paleoclimate reconstruction.Motuo located in the eastern Himalayas,exhibits a significant elevation gradient of over 7000 m from Nnamjagbarwa Peak(7782 m a.s.l.)to the Baxika(150 m a.s.l.).This region features a complete vertical zonation of vegetation,from alpine meadow to tropical forest,presenting an ideal place to investigate the relationships among vegetation,soil and climate conditions across altitudinal gradients.This study aims to explore the vertical variations in the physicochemical composition of topsoil and its relationship with temperature and precipitation.Materials and methods Twenty-seven topsoil samples were collected at 100 m intervals from 800 m to 3600 m a.s.l.along the southern slope of the Himalayas.Grain size,magnetic susceptibility and geochemical elements were measured to discuss the vertical variation characteristics of topsoil composition and their correlation with climatic factors.Results(1)The grain size of topsoil at different altitudes in Motuo is mainly composed of sand accounting for an averaged 53.2%,followed by silt and clay.(2)In the mixed forest zone,frequency dependent magnetic susceptibility(χfd%)shows a clear relationship with altitude,and clay is positively correlated with both altitude and climatic factors.(3)The oxides of topsoil in this area mainly consist of SiO_(2),Al_(2)O_(3) and Fe_(2)O_(3),followed by MgO,CaO,Na_(2)O and K_(2)O,with slight variations in the primary components at different altitudes.The sensitivity of elements to climate varies across different altitudes and vegetation zone,likely due to the region’s complex topography and vegetation.(4)Physical and biological weathering dominates in the broad-leaved forest zone of Motuo,while chemical weathering is more prominent in the coniferous forest zone,with the mixed forest zone falling in between.Discussion The formation of topsoil across the three vegetation zones is influenced by various factors,including parent material,vegetation,and climate.In the broad-leaved forest zone,physical weathering(precipitation,root wedging etc.)and pedogenesis dominate,resulting in finer grain size.The χ_(fd)% increases with altitude likely due to the high temperature and abundant precipitation in this zone,which facilitate the transformation of strong magnetic miners into weaker ones,particularly when the soil is oversaturated.Zirconium(Zr),primarily found in zircon,is depleted at lower altitudes by strong current erosion.Barium(Ba)is similarly reduced at low altitudes in this zone.In mixed forest zone,clay content is the lowest,indicating weaker physical weathering conditions than broad-leaved forest zone.The coarser grain size may result from the combined effects of topography and vegetation coverage.Magnetic susceptibility and organic matter show a positive correlation with altitude.Zr concentration is higher than that in the broad-leaved forest zone,likely resulting from decreased precipitation.In the coniferous zone,the clay content shows considerable fluctuations,with grain size generally becoming finer as altitude increases.This trend may be explained by intensified soil disintegration from seasonal freeze-thaw cycles.The χ_(fd)% values lack a clear trend or pattern,possibly due to soil erosion causing the migration of magnetic minerals or insufficient iron precipitation,which reduces the concentration of magnetic minerals in the soil.Additionally,a positive correlation is observed between altitude and organic matter content,with higher altitudes associated with greater organic matter accumulation.This may be attributed to lower microbial activity in colder conditions,which slows the decomposition and transformation of organic matter.Conclusions The variations in grain size,magnetic susceptibility,and geochemical elements differ across altitudes and vegetation zones,closely connected to the complex interplay of terrain,vegetation,and climate in Motuo.In the mixed forest,altitude has a significant impact onχfd%,and the clay component is particularly sensitive to changes in altitude,mean annual temperature,and precipitation.Zr shows a strong correlation with altitude and climate factors,making it a valuable indicator for assessing changes in atmospheric precipitation within specific altitude ranges.Recommendations and perspectives This study enhances our understanding of the relationships between the physicochemical properties of topsoil and climate conditions,offering valuable insights for paleoclimate reconstruction in Motuo.

Effect of Different Morphologies Induced by Solvent on ZIF-67 Derived Co@NC for Catalytic Phenol Hydrogenation

The Co@NC catalysts with different morphologies were prepared by two step process,solvent control growth and pyrolysis method.The polyhedral Co@NC-67P-450 catalyst has a relatively high CoNx content and exhibits excellent phenol hydrogenation activity(conversion 96.9%)at 160℃,3 MPa,which is higher than that of leaf shaped Co@NC-67L-450 catalyst(conversion 75.4%).We demonstrated Co_(3)O_(4)was reduced to the Co^(0)during the reaction.Moreover,CoNx species contribute to the superior hydrogenation activity of phenol.The Co-based catalysts can be easily recovered through the magnetic separation and performed the high stability.

Drishti Paint 3.2:a new open-source tool for both 2D and 3D segmentation

X-ray computed tomography(CT)has been an important technology in paleontology for several decades.It helps researchers to acquire detailed anatomical structures of fossils non-destructively.Despite its widespread application,developing an efficient and user-friendly method for segmenting CT data continues to be a formidable challenge in the field.Most CT data segmentation software operates on 2D interfaces,which limits flexibility for real-time adjustments in 3D segmentation.Here,we introduce Curves Mode in Drishti Paint 3.2,an open-source tool for CT data segmentation.Drishti Paint 3.2 allows users to manually or semi-automatically segment the CT data in both 2D and 3D environments,providing a novel solution for revisualizing CT data in paleontological studies.

Teffichthys wui sp. nov., a new perleidid fish from the Early Triassic of Jiangsu and Anhui, China

Perleididae is a group of stem neopterygian fishes known only from the Triassic.Here,we report the discovery of a new perleidid,Teffichthys wui sp.nov.,based on six well-preserved specimens from the late Smithian(Olenekian,Early Triassic)marine deposits of Jurong,Jiangsu and Chaohu,Anhui,China.This new discovery documents the third and youngest species of Teffichthys,which is slightly younger than the Dienerian(Induan)T.elegans from Guizhou and the early Smithian T.madagascariensis from Madagascar.The new species shows diagnostic features of Teffichthys(presence of a spiracular,38-41 lateral line scales,and no more than three epaxial rays in the caudal fin)but differs from T.madagascariensis and T.elegans in some autapomorphies(e.g.,a horizontal opercle/subopercle contact and smooth scales with a nearly straight posterior margin).The diagnostic features for the genus Teffichthys and the family Perleididae are emended based on detailed comparisons of the new taxon with other perleidids.The phylogenetic relationships of perleidids with other stem neopterygians are discussed using a cladistic approach,and the results provide new insights into the phylogeny and classification of main stem neopterygian clades.

Structure and functional heterogeneity of soil microbial communities in different farmland types on the Loess Plateau

Background,aim,and scope Soil microbes are important drivers of nutrient transformation and energy f low.Reclaiming forest land for agricultural use may have profound effects on soil properties and microbial communities.However,the response of soil microbial communities to soil reclamation in the dryland agroecosystem is less understood.Therefore,it is necessary to investigate the changes of soil microbial communities driven by land use conversion to promote nutrient cycling in reclaimed farmland.Materials and methods Based on the metagenomic technique,we evaluated the microbial composition and function of the newly created farmland(NF)after reclamation with two types of traditional farmland(slope farmland(SF),checkdam farmland(CF))on the Loess Plateau,and explored the response of nutrient cycling function to dominant genera and soil properties.Results The results showed that Proteobacteria,Actinobacteria,and Acidobacteria were prevalent in the three types of farmlands.Compared with SF and CF,NF increased the relative abundance of Actinobacteria and Nocardioides,as well as genes related to amino acid metabolism and carbohydrate metabolism.The relative abundance of functional genes related to carbon and nitrogen cycling in the NF was higher than that in the traditional farmland(SF and CF).The relative abundance of nutrient cycling functional genes was positively correlated with dominant genera in the three types of farmlands.Except for pH,soil physicochemical factors were negatively correlated with genes related to amino acid metabolism and carbon cycle.Discussion Previous studies have shown that the nutrient conditions of the soil may intensify the competition between the eutrophic and oligotrophic microbial populations.After long-term cultivation and fertilization,the soil properties of traditional farmland were significantly different from those of NF,leading to the differentiation of dominant microbial groups.Microbes usually have functional redundancy to cope with changing environments.Soil microbes in traditional farmland may contain more genes related to replication and repair,cell growth and death,and environmental adaptation in response to disturbances caused by agricultural practices.On the contrary,the NF was less disturbed by agricultural activities,and the soil properties were more similar to forest land,so the carbon and nitrogen cycle function genes were more abundant.The nutrient cycling function was affected by the abundance of microbial dominant groups and soil properties,which may be related to the availability of soil nutrients and agricultural disturbance in different farmlands.Aspects of soil microbial-driven nutrient cycling in agriculture could be regulated in sustainable method.Conclusions The change from forest land to farmland kept more carbon and nitrogen cycling function in the newly created farmland,while long-term agricultural activities have drastically changed the functional structure of traditional farmland,resulting in the nutrient cycling function more concentrated to meet the needs of crop growth.Recommendations and perspectives Hence,it is necessary to apply sustainable agricultural method to regulate microbial-driven nutrient cycling.The insights are meaningful for sustainable agricultural development and land management in arid areas.

ZNT1 Involves Cuproptosis through Regulating MTF1-conduced Expression of MT1X under Copper Overload

Industrial activities such as smelting emissions,mineral combustion and industrial wastewater discharge might lead to copper pollution in the environment.This kind of copper pollution has harmful effects on aquatic o rganisms,plants and animals through direct or indirect exposure.However,the current understanding of the toxicity of copper is rather limited.Copper overload can perturb intracellular homeostasis and induce oxidative stress and e ven cell death.Recently,cuproptosis has been identified as a copper-dependent form of cell death induced by o xidative stress in mitochondria.We uncover here that zinc transporter 1(ZNT1)is an important regulator involved in cuproptosis.Firstly,we established the copper overload-induced cell death model with the overexpression of copper importer SLC31A1 in HeLa cells.Using this model,we conducted unbiased genome-wide CRISPR-Cas9 screens in cells treated with copper.Our results revealed a significant enrichment of ZNT1 gene in both library A and library B plasmids.Knocking out of ZNT1 in HeLa cells notably prevented cuproptosis.Subsequent knockout of metal transcription factor 1(MTF1)in ZNT1-deficient cells nearly abolished their ability to resist copper-induced cell death.However,overexpression of metallothionein 1X(MT1X)in the double-knockout cells could p artially restored the resistance to cuproptosis by loss of MTF1.Mechanistically,knockout of ZNT1 could promote MT1X expression by activating MTF1.As a consequence,the interaction between MT1X and copper was e nhanced,reducing the flow of copper into mitochondria and eliminating mitochondria damage.Taken together,this study reveals the important role of ZNT1 in cuproptosis and shows MTF1-MT1X axis mediated resistance to c uproptosis.Moreover,our study will help to understand the regulatory mechanism of cellular and systemic copper homeostasis under copper overload,and present insights into novel treatments for damages caused by both genetic copper overload diseases and environmental copper contamination.

Structure and Vibrational Spectroscopy of 2-Methylallyl Alcohol

The intramolecular O−H…πhydrogen bond has garnered significant research interest in recent decades.In this work,we utilized the infrared(IR)-vacuum-ultraviolet(VUV)nonresonant ionization detected IR spectroscopy(NRID-IR)method to study the molecular structure of neutral and cationic 2-methylallyl alcohol(MAA,CH_(2)=C(CH_(3))−CH_(2)−OH).Density functional theory calculations revealed five stable neutral and three stable cationic MAA conformers,respectively.Two neutral MAA conformers are expected to have an O−H…πintramolecular hydrogen bond interaction,based on the structural characterization that the OH group is directed toward the C=C double bond.The IR spectra of both neutral(2700−3700 cm^(−1))and cationic MAA(2500−7200 cm^(−1))were measured,and the anharmonic IR spectra were calculated at the B3LYP-D3(BJ)/def2-TZVPP level.The OH stretching vibration frequency of neutral MAA was observed at 3656 cm−1,slightly lower than those of methanol and ethanol.In contrast,the OH stretching vibration of cationic MAA was red-shifted by about 140 cm^(−1)compared to neutral MAA.The interaction region indicator and natural bond orbital analysis suggest that the O−H…πinteraction in neutral MAA is weak,and may not play a major role in stabilizing the neutral MAA.

A new genus of galeaspids(jawless stem-Gnathostomata)from the early Silurian Chongqing Lagerstätte,China

The early Silurian Chongqing Lagerstätte(middle Telychian)yields exceptionally preserved articulated jawless and jawed fishes.Here,we describe a new eugaleaspiform(Galeaspida,jawless stem-Gnathostomata),Miaojiaaspis dichotomus gen.et sp.nov.,from the Chongqing Lagerstätte in Xiushan,Chongqing,China.The new form resembles Tujiaaspis vividus in the short medial dorsal canal,and the presence of the branching ends of the lateral transverse canal.They differ in that T.vividus has highly developed subordinate branches of the sensory canals that form a reticulate sensory canal system,and the median dorsal opening is more elongated.Our phylogenetic analysis recovers M.dichotomus and T.vividus as a monophyletic clade(Tujiaaspidae fam.nov.),which is supported by two synapomorphies:the short medial dorsal canal,and the branching ends of the lateral transverse canal.Tujiaaspidae forms a trichotomy with Shuyuidae and a clade comprising Anjiaspis,Sinogaleaspidae,Yongdongaspidae,and the‘eugaleaspid cluster’.The sensory canal patterns in galeaspids are compared to show the transformation sequence of the sensory canal system in Eugaleaspiformes.