Solid-state lithium(Li)batteries are hailed as the nextgeneration energy storage technology,garnering significant attention for their potential high energy density and safety.Particularly when using Li-rich manganese ...Solid-state lithium(Li)batteries are hailed as the nextgeneration energy storage technology,garnering significant attention for their potential high energy density and safety.Particularly when using Li-rich manganese layered oxide(LRMO)as cathodes(theoretical capacity exceeding250 mAh/g),energy densities over 600 Wh/kg can be theoretically achieved[1,2].展开更多
The deployment of flexible zinc-ion batteries is impeded by dendrite growth from random anode defects.Conventional defect-elimination strategies often compromise flexibility and fail to achieve uniform interfaces.We p...The deployment of flexible zinc-ion batteries is impeded by dendrite growth from random anode defects.Conventional defect-elimination strategies often compromise flexibility and fail to achieve uniform interfaces.We propose a paradigm shift:reconfiguring random defects into engineered,monodisperse artificial micro-curves to homogenize electric fields and guide aligned zinc(Zn)deposition.Using moisture-assisted flash heating,we transform zincophilic silver(Ag)coatings on carbon fibers into uniformly dispersed micro-curved particles(Ag Particles@CC),creating identical nucleation sites with optimal zinc ion(Zn^(2+))adsorption energetics.Theoretical simulations confirm these structures eliminate localized field concentrations,enabling homogeneous plating/stripping.This design demonstrates remarkable performance,with ultrastable 1500 cycles at 10 mA cm^(-2)(98.6%avg.Coulombic efficiency)and symmetric cell operation>650 h(57.7 mV hysteresis).Crucially,interparticle discontinuities preserve intrinsic flexibility,enabling flexible pouch cells(Ag Particles@CC-Zn//NaV_(3)O_(8)·1,5H_(2)O)to successfully power wearable devices such as smartwatches and smartphones.This work establishes defect reconfiguration via artificial micro-curvature engineering as a universal strategy toward dendritesuppressed,flexible energy storage.展开更多
The nonchemically amplified(nonCA)polymer resists,including ionic and nonionic types,have achieved higher resolution and smaller line edge roughness(LER)than traditional chemically amplified ones.However,for polymer r...The nonchemically amplified(nonCA)polymer resists,including ionic and nonionic types,have achieved higher resolution and smaller line edge roughness(LER)than traditional chemically amplified ones.However,for polymer resists,chain entanglement is an inevitable limitation for the further reduction of LER.To overcome this problem,it is logical to apply the nonCA concept to molecule-based resists due to their advantages of monodispersity and small size.To date,only a few examples of ionic sulfonium salts-based nonCA molecular glass resists(nonCAMGRs)have been reported.They demonstrated high resolution and small LER well,but their electron beam sensitivity seemed less than ideal.To our knowledge,non-ionic sulfoxime oxime esters-based molecular resists were not reported yet,which leaves room for new round of more in-depth reserch on nonCAMGRs.Here,employing the excellent spirobixanthene backbone,we have first designed non-ionic sulfoxime oxime esters-based nonCAMGRs X4-NI-tf and X4-NI-tfb,for comparison,sulfonium salts-based nonCAMGRs X4-I-otfdm was designed.All exhibit favorable thermal properties(T_(d,5%)>200°C)and filmforming capabilities(RMSs<0.4 nm).Via EBL,X4-I-otfdm achieved higher resolution(16 nm,LER 1.4 nm)than X4-NI-tf and X4-NI-tfb(20 nm,LER 1.6 nm).But contrast curve revealed that the sensitivity of X4-NI-tf and X4-NI-tfb(D_(100):370 and 350μC/cm^(2))was significantly higher than X4-I-otfdm(D_(100):3300μC/cm^(2)),demonstrating that the sensitivity of sulfoxime oxime esters exceeds that of sulfonium salts and introduction of bromine can further enhance the sensitivity;based on above,X4-NI-tfb exhibited the lowest Z-factor and demonstrated the best overall performance.We believe that nonCAMGRs based on sulfoxime oxime esters represent a strong candidate for high-performance photoresists.展开更多
Color filters are essential components for optical modulation.However,conventional filters are restricted to operating exclusively in either reflective or transmissive mode.Furthermore,they suffer from limited UV and ...Color filters are essential components for optical modulation.However,conventional filters are restricted to operating exclusively in either reflective or transmissive mode.Furthermore,they suffer from limited UV and thermal stability,low color purity,and exhibit identical coloration on both surfaces.Herein,we propose a novel design strategy for trans-reflective color filters by integrating the absorptive properties of dye-doped polysulfone(PSU)with the diffractive capabilities of photonic crystals.This composite filter achieved broad-spectrum transmission with deep color outputs—yellow(0.410,0.510),magenta(0.446,0.231),and cyan(0.201,0.425)—closely aligned with standard color space coordinates.By tuning the refractive index of CeO_(2)@SiO_(2)nanoparticles to match dye-based PSU matrix,the transmittance of filters exceeded 70%.Moreover,dye-mediated absorption reduces the scattering light,thereby enhancing reflection color purity(full width at half maxima(FWHM)=25 nm)and producing vibrant blue,green,and red hues.The incorporation of UV-absorbing CeO_(2)@SiO_(2)nanoparticles effectively mitigated dye photodegradation,yielding exceptional UV stability(ΔT<2%under prolonged UV exposure).The filters also exhibited outstanding thermal stability(ΔT<1%after 30 min heat treatment at 230°C).This work establishes a robust materials design framework for multifunctional optical filters,advancing the development of highfidelity dual-mode color systems for next-generation display technologies.展开更多
To fully utilize the resources provided by optical fiber networks,a cross-band quantum light source generating photon pairs,where one photon in a pair is at C band and the other is at O band,is proposed in this work.T...To fully utilize the resources provided by optical fiber networks,a cross-band quantum light source generating photon pairs,where one photon in a pair is at C band and the other is at O band,is proposed in this work.This source is based on spontaneous four-wave mixing(SFWM)in a piece of shallow-ridge silicon waveguide.Theoretical analysis shows that the waveguide dispersion could be tailored by adjusting the ridge width,enabling broadband photon pair generation by SFWM across C band and O band.The spontaneous Raman scattering(SpRS)in silicon waveguides is also investigated experimentally.It shows that there are two regions in the spectrum of generated photons from SpRS,which could be used to achieve cross-band photon pair generation.A chip of shallow-ridge silicon waveguide samples with different ridge widths has been fabricated,through which cross-band photon pair generation is demonstrated experimentally.The experimental results show that the source can be achieved using dispersion-optimized shallow-ridge silicon waveguides.This cross-band quantum light source provides a way to develop new fiber-based quantum communication functions utilizing both C band and O band and extends applications of quantum networks.展开更多
In this study,electrochemical C-H carboxylation of benzylamines with CO_(2) was reported.This linear paired electrolysis system enables efficient and economical synthesis of value-added α-amino acids(α-AAs) under mi...In this study,electrochemical C-H carboxylation of benzylamines with CO_(2) was reported.This linear paired electrolysis system enables efficient and economical synthesis of value-added α-amino acids(α-AAs) under mild conditions.Various substituted benzylamines containing diverse functional groups and even highly reactive moieties,such as cyano,amide and alkene groups could be successfully transformed to the carboxylated products.Notably,this method proved to be applicable to the late-stage modification of biorelevant compounds,highlighting its potential for synthetic chemistry.Mechanistic studies such as radical trapping experiments,kinetic isotope effect(KIE) tests and cyclic voltammetry(CV) studies provided useful insight into this transformation.展开更多
Members of genus Chrysanthemum,comprising approximately 40 species,hold economic significance as edible,medicinal,and ornamental plants.Among these species,Chrysanthemum indicum and the cultivated chrysanthemum C.mori...Members of genus Chrysanthemum,comprising approximately 40 species,hold economic significance as edible,medicinal,and ornamental plants.Among these species,Chrysanthemum indicum and the cultivated chrysanthemum C.morifolium have been used for tea and traditional Chinese medicine to treat common cold symptoms,impaired vision,dizziness,and skin irritation.The medicinal properties of chrysanthemum are primarily derived from its bioactive compounds,including flavonoids.展开更多
The combination of electrochemistry and metal catalysts has been a popular research topic in the field of organic synthesis due to the abundance and controllable valence states of transition metals,where electron tran...The combination of electrochemistry and metal catalysts has been a popular research topic in the field of organic synthesis due to the abundance and controllable valence states of transition metals,where electron transfer at the electrode produces catalysts with more valence states.Among these transition metal catalysts,electrochemical conversions catalyzed by inexpensive copper metals have received considerable attention.This article systematically investigated this field and reviewed the electrochemical copper catalytic methods applied in organic synthesis from the different activation modes of substrates,which can be broadly classified into the functionalization of C=C bonds,C-H bond activation,C-C and C-X bond activation,and so on.展开更多
While nuclear energy represents a low-carbon and high-efficiency energy source that plays a vital role in the global energy mix,the limitations of spent fuel reprocessing technology pose a major challenge to its susta...While nuclear energy represents a low-carbon and high-efficiency energy source that plays a vital role in the global energy mix,the limitations of spent fuel reprocessing technology pose a major challenge to its sustainable development.The PUREX(plutonium uranium redox extraction)process is currently the dominant nuclear fuel reprocessing technology in the world.However,the key extractant in this process is tributyl phosphate(TBP),which degrades under intense radiation,high temperatures,and strong acidity.This leads to the production of dibutyl phosphate,monobutyl phosphate,and other degradation byproducts,which may reduce the extraction efficiency and trigger third-phase formation and equipment corrosion.This paper systematically reviews the degradation mechanisms of TBP and its diluents,the analytical technique suitable for characterizing degradation products,and the impact of degradation products on the post-treatment process.Additionally,optimization strategies employed for suppressing third-phase formation are discussed.This study offers a theoretical foundation and technical insights in optimizing the PUREX process and ensuring the safe operation of the post-treatment process.展开更多
Bicyclo[2.1.1]hexanes(BCHs) are structurally unique C(sp^(3))-rich bicyclic hydrocarbons that are gaining prominence in the field of medicinal chemistry as bioisosteres of benzenoids.The nitrile is an important functi...Bicyclo[2.1.1]hexanes(BCHs) are structurally unique C(sp^(3))-rich bicyclic hydrocarbons that are gaining prominence in the field of medicinal chemistry as bioisosteres of benzenoids.The nitrile is an important functionality in drug development due to its ability to improve physicochemical and pharmacokinetic properties and facilitate potential noncovalent interactions with drug targets.Consequently,cyanoarene motifs are commonly found in drug development.The introduction of cyano-BCHs as potential bioisosteres of cyano-arenes shows great promise;however,there are currently no catalytic methods available for their synthesis.Herein,we report a palladium-catalyzed enantioselective [2σ+2π] cycloadditions of bicyclo[1.1.0]butanes with arylidenemalononitriles for the preparation of chiral cyano-BCHs.This method accommodated a wide range of substrates and tolerated various functional groups.The cyano-BCH products could be transformed to molecules with diverse functionality.Control experiments suggest that the reaction proceeds via a zwitterionic intermediate generated by palladium-mediated ring opening of vinyl-carbonyl bicyclo[1.1.0]butanes followed by stereoselective 1,2-addition and intramolecular allylic substitution reactions.展开更多
Vulnerabilities are a known problem in modern Open Source Software(OSS).Most developers often rely on third-party libraries to accelerate feature implementation.However,these libraries may contain vulnerabilities that...Vulnerabilities are a known problem in modern Open Source Software(OSS).Most developers often rely on third-party libraries to accelerate feature implementation.However,these libraries may contain vulnerabilities that attackers can exploit to propagate malicious code,posing security risks to dependent projects.Existing research addresses these challenges through Software Composition Analysis(SCA)for vulnerability detection and remediation.Nevertheless,current solutions may introduce additional issues,such as incompatibilities,dependency conflicts,and additional vulnerabilities.To address this,we propose Vulnerability Scan and Protection(VulnScanPro),a robust solution for detection and remediation vulnerabilities in Java projects.Specifically,VulnScanPro builds a finegrained method graph to identify unreachable methods.The method graph is mapped to the project’s dependency tree,constructing a comprehensive vulnerability propagation graph that identifies unreachable vulnerable APIs and dependencies.Based on this analysis,we propose three solutions for vulnerability remediation:(1)Removing unreachable vulnerable dependencies,thereby resolving security risks and reducing maintenance overhead.(2)Upgrading vulnerable dependencies to the closest non-vulnerable versions,while pinning the versions of transitive dependencies introduced by the vulnerable dependency,in order to mitigate compatibility issues and prevent the introduction of new vulnerabilities.(3)Eliminating unreachable vulnerable APIs,particularly when security patches are either incompatible or absent.Experimental results show that these solutions effectively mitigate vulnerabilities and enhance the overall security of the project.展开更多
Radical cycloaddition reactions(RCRs) are highly effective methods for constructing complex carbo-and heterocycles,which are frequently encountered in natural products that exhibit intriguing biological properties and...Radical cycloaddition reactions(RCRs) are highly effective methods for constructing complex carbo-and heterocycles,which are frequently encountered in natural products that exhibit intriguing biological properties and hold significant potential for applications in medicinal chemistry.Radical-mediated cycloaddition strategies,which recycle radical character,are particularly appealing because they require only a catalytic amount of reagent and promise reactions with theoretically high atom economy.This review focuses on recent developments and synthetic applications in RCRs,with an emphasis on visible lightinduced radical photocycloaddition reactions(RPCRs),transition metal-catalyzed approaches,and small molecule-catalyzed methods.By highlighting some outstanding innovations and addressing current challenges,this review aims to identify potential areas for improvement.These advancements will provide more efficient pathways for the synthesis of natural product molecules and offer valuable insights for the development of new synthetic methodologies.展开更多
The preparation and functionalization of polymeric capsules attract intense attention due to their application in various areas.Herein we presented an amphiphilic alternating copolymer(ACP)-based microcapsule which is...The preparation and functionalization of polymeric capsules attract intense attention due to their application in various areas.Herein we presented an amphiphilic alternating copolymer(ACP)-based microcapsule which is both robust and readily-functionalized through interfacial click polymerization.A water-in-oil emulsion was constructed to act as the reaction medium,the hydrophilic 1,3-butadiene diepoxide(BDE)in water phase reacted with the oleophilic 1,4-dibutanedithiol(BDT)in oil phase at the water-oil interface to form the amphiphilic ACP named poly(2,3-dihydroxy butylene-alt-butylene dithioether)(abbreviated as P(DHB-a-BDT)below),which would deposite in situ to form the micro-sized capsules.Significantly,the dried capsules are robust enough to be rehydrated once the water was added and almost restored their original morphologies.Further elucidation showed that the Young's modulus of these capsules exceeded 1 GPa.As long as we know,it is the first time for the mechanical properties of the ACP-based microstructures being investigated.Besides,functionalization could be achieved simultaneously with the formation process.As a proof of concept,positive-charged capsules were successfully obtained through click copolymerization.Stemming from the unique characteristics of amphiphilic ACPs which combined both merits of click chemistry and interfacial reactions,all these features of the current method as well as the resultant capsules may promote the application of the polymeric capsules.展开更多
Dentin,the main component of dental hard tissues,is produced by differentiated odontoblasts.How odontoblast differentiation is regulated remains understudied.Here,we screen that the expression of membrane-associated R...Dentin,the main component of dental hard tissues,is produced by differentiated odontoblasts.How odontoblast differentiation is regulated remains understudied.Here,we screen that the expression of membrane-associated RING finger protein 2(March2) is the highest among all March family members,with an increasing trend during odontoblast differentiation.In mouse incisors and molars,MARCH2 is moderately expressed in the undifferentiated dental papilla cells and strongly expressed in the odontoblasts.Knockdown and overexpression experiments demonstrate that MARCH2 inhibits odontoblastic differentiation of mouse dental papilla cells(mDPCs).Additionally,both March2 deficient mice and mice with odontoblast specific knockdown of March2 exhibit the phenotype of increased dentin thickness,accelerated dentin deposition as well as elevated expression levels of odontoblast markers compared with control littermates.Therefore,MARCH2 plays an inhibitory role in odontoblast differentiation.Mechanistically,MARCH2 interacts with protein tyrosine phosphatase receptor delta(PTPRD) and facilitates its K27-linked polyubiquitination and subsequent degradation,which is dependent on the ligase activity of MARCH2.The presence of MARCH2promotes the translocation of PTPRD from the cell membrane to the lysosome,thereby enhancing its degradation via the lysosomal pathway.Further experiments show that knockdown of endogenous Ptprd impairs odontoblastic differentiation of mDPCs.Ptprd and March2 double knockdown in mDPCs apparently reversed the enhanced odontoblastic differentiation by knockdown of March2 alone,indicating that MARCH2 inhibits odontoblastic differentiation by promoting PTPRD degradation.This study unveils a novel mechanism where an E3 ubiquitin ligase regulates odontoblast differentiation through post-translational modification of a membrane protein,highlighting a promising direction for future exploration.展开更多
Aqueous zinc-ion batteries have emerged as highly promising energy storage devices due to their high theoretical capacity,low cost,and high safety.However,they still suffer from dendrite growth and parasitic side reac...Aqueous zinc-ion batteries have emerged as highly promising energy storage devices due to their high theoretical capacity,low cost,and high safety.However,they still suffer from dendrite growth and parasitic side reactions caused by reactive aqueous electrolytes,which not only compromise reversibility but may also lead to internal short circuits,severely limiting practical applications.Herein,inulin(INU),a hydroxyl-rich polysaccharide,is proposed as a multifunctional electrolyte additive.Experimental and density functional theory calculations reveal that INU molecules effectively disrupt the original hydrogen-bond network,facilitating Zn^(2+)desolvation and rapid migration,thereby effectively resisting hydrogen evolution reaction,Zn corrosion,and by-products formation.Additionally,INU preferentially adsorbs on the Zn(002)crystal plane,forming a hydrophobic protective layer and guiding uniform Zn^(2+)deposition,thus inhibiting random dendritic growth.The presence of INU also effectively retards the dissolution process of V_(2)O_(5).As a result,the Zn‖Zn symmetric cell assembled with INU-3 electrolyte achieves an extended cycling life of 2400 h at a current density of 0.5 mA cm^(-2) and an areal capacity of0.5 mAh m^(-2).Furthermore,the Zn‖V_(2)O_(5) full cell exhibits a high capacity of 386.0 mAh g^(-1) at0.5 A g^(-1) and a high capacity retention of 55.26%at 8 A g^(-1).The full cell maintains remarkable capacity retention of 73%after 500 cycles at 1 A g^(-1) and 91%after 1000 cycles at 3 A g^(-1).This work inspires the study of electrolyte additives for aqueous zinc-ion batteries.展开更多
The absence of large-size gallium nitride(GaN) substrates with low dislocation density remains a primary bottleneck for advancing GaN-based devices. Here, we demonstrate the achievement of 8-inch freestanding GaN subs...The absence of large-size gallium nitride(GaN) substrates with low dislocation density remains a primary bottleneck for advancing GaN-based devices. Here, we demonstrate the achievement of 8-inch freestanding GaN substrates grown by hydride vapor phase epitaxy. Critical to this achievement is the improvement in gas-flow uniformity, which ensures exceptional thickness homogeneity and enables the crack-free growth of GaN. After laser lift-off(LLO) separation, the freestanding GaN substrate exhibits superior crystal quality, evidenced by full width at half maximum values of 68 and 54 arcsec for X-ray diffraction rocking curves of(002) and(102) planes, alongside a low dislocation density of 1.6 × 10^(6) cm^(-2). This approach establishes a robust pathway for the production of large-size GaN substrates, which are essential for advancing next-generation power electronics and high-efficiency photonics.展开更多
Freshwater scarcity is exacerbated by uneven distribution of limited freshwater resources and high energy costs of desalination technologies.Atmospheric water vapor,a vast and geographically unrestricted reservoir,cou...Freshwater scarcity is exacerbated by uneven distribution of limited freshwater resources and high energy costs of desalination technologies.Atmospheric water vapor,a vast and geographically unrestricted reservoir,could become a sustainable alternative.Sorption-based atmospheric water harvesting(SAWH)has emerged as an available solution,yet conventional desorption methods relying on energy-intensive electrical heating hinder its scalability.Herein,a photothermal hygroscopic sponge has been developed for solar-driven atmospheric water harvesting.The composites combine a malleable melamine sponge skeleton,lithium chloride as a hygroscopic agent,and hydrangea-like molybdenum disulfide as a photothermal component,forming a multiscale“pore-film”cross-linked structure by an eco-friendly immersion-freeze-drying method.The optimized sample achieves exceptional hygroscopic capacity(3.92 g/g at 90%RH)and freshwater production efficiency(87.77%),which is attributed to synergistic effects of porous skeleton based crosslinked structures and“pore-film”structures,and outstanding photothermal conversion efficiency of MoS2.The unique structure could stabilize LiCl to prevent leakage,increase mass transfer effectiveness of whole SWAH process,and enable flexibility for diverse applications.We carried out outdoor experiments to demonstrate a solar-driven water production rate of 4.22 L m-2 d-1 without external energy input.This work provides insights into sustainable freshwater generation and promotes green energy utilization in addressing global water scarcity.展开更多
The stimulator of interferon genes(STING),as a critical innate immune sensor,has been widely and continually explored in immune-related disease treatment.As lipid bilayer-closed particles derived from cells,extracellu...The stimulator of interferon genes(STING),as a critical innate immune sensor,has been widely and continually explored in immune-related disease treatment.As lipid bilayer-closed particles derived from cells,extracellular vesicles(EVs)inherently function in target-guided intercellular communication.To incorporate the native merits of EVs into STING pathways,i.e.,engineered EV@STING,poor bioavailability and off-target issues that STING activators possess could be significantly overcome.In this review,emerged STING activators such as nitrogen-containing heterocyclic structures and the universal STING activation strategy(uniSTING)are firstly summarized.Diverse EVs sources from mesenchymal stem cells(MSCs)and innate and adaptive immune cells may evoke distinct regulatory results.Concurrently,how the EVs contents including double-stranded DNA(dsDNA),microRNA(miRNA),cyclic GMP-AMP synthase(cGAS)and 2′3′-cyclic GMP-AMP(2′3′-cGAMP)proteins participate in the regulation of STING activation are widely studied.After mastering the two pivotal aspects of EV@STING,their immunomodulatory roles including in pathogen infection,inflammatory diseases,and cancer therapy are comprehensively summed up and discussed.Finally,in cancer study field,therapeutic challenges and clinical translational opportunities of EV@STING are thoroughly evaluated.展开更多
Fabricating macroscale smart actuators that can convert light energy into other forms of energy,especially mechanical and electrical energy,is of great significance.Herein,a simple and efficient 4D printed method for ...Fabricating macroscale smart actuators that can convert light energy into other forms of energy,especially mechanical and electrical energy,is of great significance.Herein,a simple and efficient 4D printed method for fabricating photomechanical actuators based on micro/nano-scale crystals is developed.The high versatility and generality of this method are successfully demonstrated using nine different types of photoresponsive crystalline actuators,including acylhydrazone-,anthracene-,olefin-,and azobenzene-based molecular crystals and covalent organic frameworks(COFs).The low-cost neutral silicone sealant elastomer is first chosen as the photomechanical 4D printing matrix.Notably,these actuators can be used to perform bionic motions(the first windmills spin using crystalline material,dragonflies fly,and sunflowers bloom)under the stimulation of visible light and can realize energy conversion from mechanical energy into electricity when coupled with a piezoelectric membrane.This work provides new insights into the design and manufacturing of smart photomechanical actuators and electricity generators and expands the application scope of COFs.展开更多
Methanol,a crucial C1 intermediate,bridges traditional fossil-based chemical processes with emerging sustainable catalytic technologies by serving as both a versatile hydrogenation product from CO/CO_(2)and an active ...Methanol,a crucial C1 intermediate,bridges traditional fossil-based chemical processes with emerging sustainable catalytic technologies by serving as both a versatile hydrogenation product from CO/CO_(2)and an active intermediate for hydrocarbon synthesis.Despite significant progress in methanol-to-hydrocarbon(MTH)conversion,a comprehensive understanding of reaction mechanisms remains essential to enhance catalyst design and industrial applicability.This review critically synthesizes recent advances in mechanistic insights related to methanol conversion and methanol-mediated catalytic processes.Firstly,we systematically outline key reaction pathways involved in initial carbon–carbon(C–C)bond formation through direct and indirect mechanisms,emphasizing significant breakthroughs from spectroscopic analyses and theoretical calculations.Subsequently,we highlight the autocatalytic characteristics and dual-cycle mechanisms underlying MTH processes,critically evaluating the roles of zeolite structures,pore sizes,topology,and acidity in governing product selectivity and catalyst stability.Additionally,we discuss cutting-edge developments in tandem catalytic systems employing methanol as a pivotal intermediate for CO_(x)hydrogenation,emphasizing the transferable mechanistic principles and catalytic insights.Finally,we identify future research directions,including elucidating precise hydrocarbon pool(HCP)intermediates,optimizing zeolite structures through computational-guided design,and developing robust catalytic systems leveraging advanced characterization methods and artificial intelligence.By integrating multidisciplinary approaches from catalytic science,materials engineering,and reaction engineering,this review provides actionable guidance towards rational design and optimization of advanced catalytic systems for efficient methanol conversion processes.展开更多
基金supported by the National Natural Science Foundation of China(No.22479021).
文摘Solid-state lithium(Li)batteries are hailed as the nextgeneration energy storage technology,garnering significant attention for their potential high energy density and safety.Particularly when using Li-rich manganese layered oxide(LRMO)as cathodes(theoretical capacity exceeding250 mAh/g),energy densities over 600 Wh/kg can be theoretically achieved[1,2].
基金supported by the National Natural Science Foundation of China(52202218)the Fundamental Research Funds for the Central Universities(CUSF-DH-T-2023044)。
文摘The deployment of flexible zinc-ion batteries is impeded by dendrite growth from random anode defects.Conventional defect-elimination strategies often compromise flexibility and fail to achieve uniform interfaces.We propose a paradigm shift:reconfiguring random defects into engineered,monodisperse artificial micro-curves to homogenize electric fields and guide aligned zinc(Zn)deposition.Using moisture-assisted flash heating,we transform zincophilic silver(Ag)coatings on carbon fibers into uniformly dispersed micro-curved particles(Ag Particles@CC),creating identical nucleation sites with optimal zinc ion(Zn^(2+))adsorption energetics.Theoretical simulations confirm these structures eliminate localized field concentrations,enabling homogeneous plating/stripping.This design demonstrates remarkable performance,with ultrastable 1500 cycles at 10 mA cm^(-2)(98.6%avg.Coulombic efficiency)and symmetric cell operation>650 h(57.7 mV hysteresis).Crucially,interparticle discontinuities preserve intrinsic flexibility,enabling flexible pouch cells(Ag Particles@CC-Zn//NaV_(3)O_(8)·1,5H_(2)O)to successfully power wearable devices such as smartwatches and smartphones.This work establishes defect reconfiguration via artificial micro-curvature engineering as a universal strategy toward dendritesuppressed,flexible energy storage.
基金supported by the National Natural Science Foundation of China(No.22278059,22174009,22078047)Fundamental Research Funds for the Central Universities(No.DUT24ZD119,DUT22LAB601 and DUT22LAB608).
文摘The nonchemically amplified(nonCA)polymer resists,including ionic and nonionic types,have achieved higher resolution and smaller line edge roughness(LER)than traditional chemically amplified ones.However,for polymer resists,chain entanglement is an inevitable limitation for the further reduction of LER.To overcome this problem,it is logical to apply the nonCA concept to molecule-based resists due to their advantages of monodispersity and small size.To date,only a few examples of ionic sulfonium salts-based nonCA molecular glass resists(nonCAMGRs)have been reported.They demonstrated high resolution and small LER well,but their electron beam sensitivity seemed less than ideal.To our knowledge,non-ionic sulfoxime oxime esters-based molecular resists were not reported yet,which leaves room for new round of more in-depth reserch on nonCAMGRs.Here,employing the excellent spirobixanthene backbone,we have first designed non-ionic sulfoxime oxime esters-based nonCAMGRs X4-NI-tf and X4-NI-tfb,for comparison,sulfonium salts-based nonCAMGRs X4-I-otfdm was designed.All exhibit favorable thermal properties(T_(d,5%)>200°C)and filmforming capabilities(RMSs<0.4 nm).Via EBL,X4-I-otfdm achieved higher resolution(16 nm,LER 1.4 nm)than X4-NI-tf and X4-NI-tfb(20 nm,LER 1.6 nm).But contrast curve revealed that the sensitivity of X4-NI-tf and X4-NI-tfb(D_(100):370 and 350μC/cm^(2))was significantly higher than X4-I-otfdm(D_(100):3300μC/cm^(2)),demonstrating that the sensitivity of sulfoxime oxime esters exceeds that of sulfonium salts and introduction of bromine can further enhance the sensitivity;based on above,X4-NI-tfb exhibited the lowest Z-factor and demonstrated the best overall performance.We believe that nonCAMGRs based on sulfoxime oxime esters represent a strong candidate for high-performance photoresists.
基金supported by the Program of the National Natural Science Foundation of China(22238002)the Fundamental Research Funds for the Central Universities(DUT22-LAB610)Research and Innovation Team Project of Dalian University of Technology(DUT2022TB10).
文摘Color filters are essential components for optical modulation.However,conventional filters are restricted to operating exclusively in either reflective or transmissive mode.Furthermore,they suffer from limited UV and thermal stability,low color purity,and exhibit identical coloration on both surfaces.Herein,we propose a novel design strategy for trans-reflective color filters by integrating the absorptive properties of dye-doped polysulfone(PSU)with the diffractive capabilities of photonic crystals.This composite filter achieved broad-spectrum transmission with deep color outputs—yellow(0.410,0.510),magenta(0.446,0.231),and cyan(0.201,0.425)—closely aligned with standard color space coordinates.By tuning the refractive index of CeO_(2)@SiO_(2)nanoparticles to match dye-based PSU matrix,the transmittance of filters exceeded 70%.Moreover,dye-mediated absorption reduces the scattering light,thereby enhancing reflection color purity(full width at half maxima(FWHM)=25 nm)and producing vibrant blue,green,and red hues.The incorporation of UV-absorbing CeO_(2)@SiO_(2)nanoparticles effectively mitigated dye photodegradation,yielding exceptional UV stability(ΔT<2%under prolonged UV exposure).The filters also exhibited outstanding thermal stability(ΔT<1%after 30 min heat treatment at 230°C).This work establishes a robust materials design framework for multifunctional optical filters,advancing the development of highfidelity dual-mode color systems for next-generation display technologies.
基金supported by the Quantum Science and Technology-National Science and Technology Major Project (Grant No.2024ZD0302502 for WZ)the National Natural Science Foundation of China(Grant No.92365210 for WZ)+1 种基金Tsinghua Initiative Scientific Research Program (for WZ)the project of Tsinghua University-Zhuhai Huafa Industrial Share Company Joint Institute for Architecture Optoelectronic Technologies (JIAOT,for YH)。
文摘To fully utilize the resources provided by optical fiber networks,a cross-band quantum light source generating photon pairs,where one photon in a pair is at C band and the other is at O band,is proposed in this work.This source is based on spontaneous four-wave mixing(SFWM)in a piece of shallow-ridge silicon waveguide.Theoretical analysis shows that the waveguide dispersion could be tailored by adjusting the ridge width,enabling broadband photon pair generation by SFWM across C band and O band.The spontaneous Raman scattering(SpRS)in silicon waveguides is also investigated experimentally.It shows that there are two regions in the spectrum of generated photons from SpRS,which could be used to achieve cross-band photon pair generation.A chip of shallow-ridge silicon waveguide samples with different ridge widths has been fabricated,through which cross-band photon pair generation is demonstrated experimentally.The experimental results show that the source can be achieved using dispersion-optimized shallow-ridge silicon waveguides.This cross-band quantum light source provides a way to develop new fiber-based quantum communication functions utilizing both C band and O band and extends applications of quantum networks.
基金Financial support from National Key R&D Program of China (No.2023YFA1507203)National Natural Science Foundation of China (Nos.22371149 and 22188101)+3 种基金the Fundamental Research Funds for the Central Universities (No.63224098)Frontiers Science Center for New Organic Matter,Nankai University (No.63181206)Nankai University are gratefully acknowledgedthe Haihe Laboratory of Sustainable Chemical Transformations for financial support。
文摘In this study,electrochemical C-H carboxylation of benzylamines with CO_(2) was reported.This linear paired electrolysis system enables efficient and economical synthesis of value-added α-amino acids(α-AAs) under mild conditions.Various substituted benzylamines containing diverse functional groups and even highly reactive moieties,such as cyano,amide and alkene groups could be successfully transformed to the carboxylated products.Notably,this method proved to be applicable to the late-stage modification of biorelevant compounds,highlighting its potential for synthetic chemistry.Mechanistic studies such as radical trapping experiments,kinetic isotope effect(KIE) tests and cyclic voltammetry(CV) studies provided useful insight into this transformation.
基金supported by The Scientific and technological innovation capacity building project of Beijing Academy of Agriculture and Forestry Sciences(Grant Nos.KJCX20251011,PT2025-31)the National Natural Science Foundation of China(Grant No.32402610)Chinese Universities Scientific Fund(Grant Nos.2024TC162,2025TC154).
文摘Members of genus Chrysanthemum,comprising approximately 40 species,hold economic significance as edible,medicinal,and ornamental plants.Among these species,Chrysanthemum indicum and the cultivated chrysanthemum C.morifolium have been used for tea and traditional Chinese medicine to treat common cold symptoms,impaired vision,dizziness,and skin irritation.The medicinal properties of chrysanthemum are primarily derived from its bioactive compounds,including flavonoids.
基金supported by the National Natural Science Foundation of China (No.22271166)the Frontiers Science Center for New Organic Matter,Nankai University (No.63181206) for generous financial support for our programs。
文摘The combination of electrochemistry and metal catalysts has been a popular research topic in the field of organic synthesis due to the abundance and controllable valence states of transition metals,where electron transfer at the electrode produces catalysts with more valence states.Among these transition metal catalysts,electrochemical conversions catalyzed by inexpensive copper metals have received considerable attention.This article systematically investigated this field and reviewed the electrochemical copper catalytic methods applied in organic synthesis from the different activation modes of substrates,which can be broadly classified into the functionalization of C=C bonds,C-H bond activation,C-C and C-X bond activation,and so on.
基金supported by the Youth Talent Project of China Nuclear Power Engineering Co.,Ltd.(KY24045).
文摘While nuclear energy represents a low-carbon and high-efficiency energy source that plays a vital role in the global energy mix,the limitations of spent fuel reprocessing technology pose a major challenge to its sustainable development.The PUREX(plutonium uranium redox extraction)process is currently the dominant nuclear fuel reprocessing technology in the world.However,the key extractant in this process is tributyl phosphate(TBP),which degrades under intense radiation,high temperatures,and strong acidity.This leads to the production of dibutyl phosphate,monobutyl phosphate,and other degradation byproducts,which may reduce the extraction efficiency and trigger third-phase formation and equipment corrosion.This paper systematically reviews the degradation mechanisms of TBP and its diluents,the analytical technique suitable for characterizing degradation products,and the impact of degradation products on the post-treatment process.Additionally,optimization strategies employed for suppressing third-phase formation are discussed.This study offers a theoretical foundation and technical insights in optimizing the PUREX process and ensuring the safe operation of the post-treatment process.
基金funding support from the National Key R&D Program of China (Nos.2022YFA1503703,2023YFA1506700)the National Natural Science Foundation of China (Nos.22071118,22271162)the Haihe Laboratory of Sustainable Chemical Transformations and the Fundamental Research Funds for the Central Universities for financial support。
文摘Bicyclo[2.1.1]hexanes(BCHs) are structurally unique C(sp^(3))-rich bicyclic hydrocarbons that are gaining prominence in the field of medicinal chemistry as bioisosteres of benzenoids.The nitrile is an important functionality in drug development due to its ability to improve physicochemical and pharmacokinetic properties and facilitate potential noncovalent interactions with drug targets.Consequently,cyanoarene motifs are commonly found in drug development.The introduction of cyano-BCHs as potential bioisosteres of cyano-arenes shows great promise;however,there are currently no catalytic methods available for their synthesis.Herein,we report a palladium-catalyzed enantioselective [2σ+2π] cycloadditions of bicyclo[1.1.0]butanes with arylidenemalononitriles for the preparation of chiral cyano-BCHs.This method accommodated a wide range of substrates and tolerated various functional groups.The cyano-BCH products could be transformed to molecules with diverse functionality.Control experiments suggest that the reaction proceeds via a zwitterionic intermediate generated by palladium-mediated ring opening of vinyl-carbonyl bicyclo[1.1.0]butanes followed by stereoselective 1,2-addition and intramolecular allylic substitution reactions.
基金supported by the National Natural Science Foundation of China(Grant No.62141210)the Fundamental Research Funds for the Central Universities(Grant No.N2217005)+1 种基金Open Fund of State Key Lab.for Novel Software Technology,Nanjing University(KFKT2021B01)111 Project(B16009).
文摘Vulnerabilities are a known problem in modern Open Source Software(OSS).Most developers often rely on third-party libraries to accelerate feature implementation.However,these libraries may contain vulnerabilities that attackers can exploit to propagate malicious code,posing security risks to dependent projects.Existing research addresses these challenges through Software Composition Analysis(SCA)for vulnerability detection and remediation.Nevertheless,current solutions may introduce additional issues,such as incompatibilities,dependency conflicts,and additional vulnerabilities.To address this,we propose Vulnerability Scan and Protection(VulnScanPro),a robust solution for detection and remediation vulnerabilities in Java projects.Specifically,VulnScanPro builds a finegrained method graph to identify unreachable methods.The method graph is mapped to the project’s dependency tree,constructing a comprehensive vulnerability propagation graph that identifies unreachable vulnerable APIs and dependencies.Based on this analysis,we propose three solutions for vulnerability remediation:(1)Removing unreachable vulnerable dependencies,thereby resolving security risks and reducing maintenance overhead.(2)Upgrading vulnerable dependencies to the closest non-vulnerable versions,while pinning the versions of transitive dependencies introduced by the vulnerable dependency,in order to mitigate compatibility issues and prevent the introduction of new vulnerabilities.(3)Eliminating unreachable vulnerable APIs,particularly when security patches are either incompatible or absent.Experimental results show that these solutions effectively mitigate vulnerabilities and enhance the overall security of the project.
基金The financial support from the National Natural Science Foundation of China (Nos.22150410339,W2432012,22301237 and 22171218)the Ministry of Science and Technology China (No.wgxz2022188) is greatly acknowledged。
文摘Radical cycloaddition reactions(RCRs) are highly effective methods for constructing complex carbo-and heterocycles,which are frequently encountered in natural products that exhibit intriguing biological properties and hold significant potential for applications in medicinal chemistry.Radical-mediated cycloaddition strategies,which recycle radical character,are particularly appealing because they require only a catalytic amount of reagent and promise reactions with theoretically high atom economy.This review focuses on recent developments and synthetic applications in RCRs,with an emphasis on visible lightinduced radical photocycloaddition reactions(RPCRs),transition metal-catalyzed approaches,and small molecule-catalyzed methods.By highlighting some outstanding innovations and addressing current challenges,this review aims to identify potential areas for improvement.These advancements will provide more efficient pathways for the synthesis of natural product molecules and offer valuable insights for the development of new synthetic methodologies.
基金financially supported by the Fundamental Research Funds for Central Universities(No.24D110627)。
文摘The preparation and functionalization of polymeric capsules attract intense attention due to their application in various areas.Herein we presented an amphiphilic alternating copolymer(ACP)-based microcapsule which is both robust and readily-functionalized through interfacial click polymerization.A water-in-oil emulsion was constructed to act as the reaction medium,the hydrophilic 1,3-butadiene diepoxide(BDE)in water phase reacted with the oleophilic 1,4-dibutanedithiol(BDT)in oil phase at the water-oil interface to form the amphiphilic ACP named poly(2,3-dihydroxy butylene-alt-butylene dithioether)(abbreviated as P(DHB-a-BDT)below),which would deposite in situ to form the micro-sized capsules.Significantly,the dried capsules are robust enough to be rehydrated once the water was added and almost restored their original morphologies.Further elucidation showed that the Young's modulus of these capsules exceeded 1 GPa.As long as we know,it is the first time for the mechanical properties of the ACP-based microstructures being investigated.Besides,functionalization could be achieved simultaneously with the formation process.As a proof of concept,positive-charged capsules were successfully obtained through click copolymerization.Stemming from the unique characteristics of amphiphilic ACPs which combined both merits of click chemistry and interfacial reactions,all these features of the current method as well as the resultant capsules may promote the application of the polymeric capsules.
基金supported by grants from the National Natural Science Foundation of China (82370913,82170914 to Guohua Yuan and 82270947 to Guobin Yang)the National Natural Science Foundation of China Key Program (82230029 to Z.C)+1 种基金the Fundamental Research Funds for the Central Universities (2042022dx0003)the Innovation Project of Municipal Science and Technology Bureau (2023020201010170) to Guohua Yuan。
文摘Dentin,the main component of dental hard tissues,is produced by differentiated odontoblasts.How odontoblast differentiation is regulated remains understudied.Here,we screen that the expression of membrane-associated RING finger protein 2(March2) is the highest among all March family members,with an increasing trend during odontoblast differentiation.In mouse incisors and molars,MARCH2 is moderately expressed in the undifferentiated dental papilla cells and strongly expressed in the odontoblasts.Knockdown and overexpression experiments demonstrate that MARCH2 inhibits odontoblastic differentiation of mouse dental papilla cells(mDPCs).Additionally,both March2 deficient mice and mice with odontoblast specific knockdown of March2 exhibit the phenotype of increased dentin thickness,accelerated dentin deposition as well as elevated expression levels of odontoblast markers compared with control littermates.Therefore,MARCH2 plays an inhibitory role in odontoblast differentiation.Mechanistically,MARCH2 interacts with protein tyrosine phosphatase receptor delta(PTPRD) and facilitates its K27-linked polyubiquitination and subsequent degradation,which is dependent on the ligase activity of MARCH2.The presence of MARCH2promotes the translocation of PTPRD from the cell membrane to the lysosome,thereby enhancing its degradation via the lysosomal pathway.Further experiments show that knockdown of endogenous Ptprd impairs odontoblastic differentiation of mDPCs.Ptprd and March2 double knockdown in mDPCs apparently reversed the enhanced odontoblastic differentiation by knockdown of March2 alone,indicating that MARCH2 inhibits odontoblastic differentiation by promoting PTPRD degradation.This study unveils a novel mechanism where an E3 ubiquitin ligase regulates odontoblast differentiation through post-translational modification of a membrane protein,highlighting a promising direction for future exploration.
基金the financial support by the National Natural Science Foundation of China(No.52573221,U2330124,U20A2072,52072352,21875226)the Foundation for the Youth S&T Innovation Team of Sichuan Province(2020JDTD0035)+1 种基金the Scientific Research Funds for Central Universities(ZYGX2025XJ016)the Sichuan Science and Technology Program(2023ZYD0026)。
文摘Aqueous zinc-ion batteries have emerged as highly promising energy storage devices due to their high theoretical capacity,low cost,and high safety.However,they still suffer from dendrite growth and parasitic side reactions caused by reactive aqueous electrolytes,which not only compromise reversibility but may also lead to internal short circuits,severely limiting practical applications.Herein,inulin(INU),a hydroxyl-rich polysaccharide,is proposed as a multifunctional electrolyte additive.Experimental and density functional theory calculations reveal that INU molecules effectively disrupt the original hydrogen-bond network,facilitating Zn^(2+)desolvation and rapid migration,thereby effectively resisting hydrogen evolution reaction,Zn corrosion,and by-products formation.Additionally,INU preferentially adsorbs on the Zn(002)crystal plane,forming a hydrophobic protective layer and guiding uniform Zn^(2+)deposition,thus inhibiting random dendritic growth.The presence of INU also effectively retards the dissolution process of V_(2)O_(5).As a result,the Zn‖Zn symmetric cell assembled with INU-3 electrolyte achieves an extended cycling life of 2400 h at a current density of 0.5 mA cm^(-2) and an areal capacity of0.5 mAh m^(-2).Furthermore,the Zn‖V_(2)O_(5) full cell exhibits a high capacity of 386.0 mAh g^(-1) at0.5 A g^(-1) and a high capacity retention of 55.26%at 8 A g^(-1).The full cell maintains remarkable capacity retention of 73%after 500 cycles at 1 A g^(-1) and 91%after 1000 cycles at 3 A g^(-1).This work inspires the study of electrolyte additives for aqueous zinc-ion batteries.
基金supported by the National Key Research and Development Program of China (Nos. 2022YFB3605203 and 2022YFB3608100)the National Natural Science Foundation of China (Nos. 62321004, 62227817, and 62374001)。
文摘The absence of large-size gallium nitride(GaN) substrates with low dislocation density remains a primary bottleneck for advancing GaN-based devices. Here, we demonstrate the achievement of 8-inch freestanding GaN substrates grown by hydride vapor phase epitaxy. Critical to this achievement is the improvement in gas-flow uniformity, which ensures exceptional thickness homogeneity and enables the crack-free growth of GaN. After laser lift-off(LLO) separation, the freestanding GaN substrate exhibits superior crystal quality, evidenced by full width at half maximum values of 68 and 54 arcsec for X-ray diffraction rocking curves of(002) and(102) planes, alongside a low dislocation density of 1.6 × 10^(6) cm^(-2). This approach establishes a robust pathway for the production of large-size GaN substrates, which are essential for advancing next-generation power electronics and high-efficiency photonics.
基金supported by the National Key Research and Development Program of China(No.2022YFC3702800)the National Natural Science Foundation of China(Nos.22366008,22406032)the Guizhou Provincial Basic Research Program(Natural Science)(No.ZK(2023)045).
文摘Freshwater scarcity is exacerbated by uneven distribution of limited freshwater resources and high energy costs of desalination technologies.Atmospheric water vapor,a vast and geographically unrestricted reservoir,could become a sustainable alternative.Sorption-based atmospheric water harvesting(SAWH)has emerged as an available solution,yet conventional desorption methods relying on energy-intensive electrical heating hinder its scalability.Herein,a photothermal hygroscopic sponge has been developed for solar-driven atmospheric water harvesting.The composites combine a malleable melamine sponge skeleton,lithium chloride as a hygroscopic agent,and hydrangea-like molybdenum disulfide as a photothermal component,forming a multiscale“pore-film”cross-linked structure by an eco-friendly immersion-freeze-drying method.The optimized sample achieves exceptional hygroscopic capacity(3.92 g/g at 90%RH)and freshwater production efficiency(87.77%),which is attributed to synergistic effects of porous skeleton based crosslinked structures and“pore-film”structures,and outstanding photothermal conversion efficiency of MoS2.The unique structure could stabilize LiCl to prevent leakage,increase mass transfer effectiveness of whole SWAH process,and enable flexibility for diverse applications.We carried out outdoor experiments to demonstrate a solar-driven water production rate of 4.22 L m-2 d-1 without external energy input.This work provides insights into sustainable freshwater generation and promotes green energy utilization in addressing global water scarcity.
基金supported by the National Natural Science Foundation of China(NSFC,Nos.32222090,32101069 and 32171318)Faculty of Health Sciences,University of Macao,the Multi-Year Research Grant(MYRG)of University of Macao+3 种基金the University of Macao Development Foundation(UMDF)(Nos.MYRG2022-00011-FHS and MYRG-GRG2023-00013-FHS-UMDF)the Science and Technology Development Fund,Macao SAR(Nos.0002/2021/AKP,0133/2022/A3,0009/2022/AKP,and 0006/2023/ITP1)Ministry of Education Frontiers Science Centre for Precision Oncology,University of Macao(No.SP2023-00001-FSCPO)Guangdong Provincial Applied Science and Technology Research and Development Program(No.2024A1515011140).
文摘The stimulator of interferon genes(STING),as a critical innate immune sensor,has been widely and continually explored in immune-related disease treatment.As lipid bilayer-closed particles derived from cells,extracellular vesicles(EVs)inherently function in target-guided intercellular communication.To incorporate the native merits of EVs into STING pathways,i.e.,engineered EV@STING,poor bioavailability and off-target issues that STING activators possess could be significantly overcome.In this review,emerged STING activators such as nitrogen-containing heterocyclic structures and the universal STING activation strategy(uniSTING)are firstly summarized.Diverse EVs sources from mesenchymal stem cells(MSCs)and innate and adaptive immune cells may evoke distinct regulatory results.Concurrently,how the EVs contents including double-stranded DNA(dsDNA),microRNA(miRNA),cyclic GMP-AMP synthase(cGAS)and 2′3′-cyclic GMP-AMP(2′3′-cGAMP)proteins participate in the regulation of STING activation are widely studied.After mastering the two pivotal aspects of EV@STING,their immunomodulatory roles including in pathogen infection,inflammatory diseases,and cancer therapy are comprehensively summed up and discussed.Finally,in cancer study field,therapeutic challenges and clinical translational opportunities of EV@STING are thoroughly evaluated.
基金the National Natural Science Foundation of China(22175099,22205116,22301147)National Key Research and Development Program of China(2021YFC2102100)+1 种基金Frontiers Science Center for New Organic Matter of Nankai University(63181206)111 Project(B12015).
文摘Fabricating macroscale smart actuators that can convert light energy into other forms of energy,especially mechanical and electrical energy,is of great significance.Herein,a simple and efficient 4D printed method for fabricating photomechanical actuators based on micro/nano-scale crystals is developed.The high versatility and generality of this method are successfully demonstrated using nine different types of photoresponsive crystalline actuators,including acylhydrazone-,anthracene-,olefin-,and azobenzene-based molecular crystals and covalent organic frameworks(COFs).The low-cost neutral silicone sealant elastomer is first chosen as the photomechanical 4D printing matrix.Notably,these actuators can be used to perform bionic motions(the first windmills spin using crystalline material,dragonflies fly,and sunflowers bloom)under the stimulation of visible light and can realize energy conversion from mechanical energy into electricity when coupled with a piezoelectric membrane.This work provides new insights into the design and manufacturing of smart photomechanical actuators and electricity generators and expands the application scope of COFs.
基金the Inner Mongolia Natural Science Foundation(2023ZD05,2025JQ028,2025MS02001)the National Natural Science Foundation of China(22278238,22238004)+3 种基金the National Key Research and Development Program of China(2024YFE0211400)the Major Science and Technology Program of Inner Mongolia Autonomous Region(20212120326)the“Elite Talents Revitalize Inner Mongolia”Initiative–Tier-1 Talent Team(202410)the Ordos Science and Technology Breakthrough(JBGS2024003),and Ordos Laboratory for their financial support.
文摘Methanol,a crucial C1 intermediate,bridges traditional fossil-based chemical processes with emerging sustainable catalytic technologies by serving as both a versatile hydrogenation product from CO/CO_(2)and an active intermediate for hydrocarbon synthesis.Despite significant progress in methanol-to-hydrocarbon(MTH)conversion,a comprehensive understanding of reaction mechanisms remains essential to enhance catalyst design and industrial applicability.This review critically synthesizes recent advances in mechanistic insights related to methanol conversion and methanol-mediated catalytic processes.Firstly,we systematically outline key reaction pathways involved in initial carbon–carbon(C–C)bond formation through direct and indirect mechanisms,emphasizing significant breakthroughs from spectroscopic analyses and theoretical calculations.Subsequently,we highlight the autocatalytic characteristics and dual-cycle mechanisms underlying MTH processes,critically evaluating the roles of zeolite structures,pore sizes,topology,and acidity in governing product selectivity and catalyst stability.Additionally,we discuss cutting-edge developments in tandem catalytic systems employing methanol as a pivotal intermediate for CO_(x)hydrogenation,emphasizing the transferable mechanistic principles and catalytic insights.Finally,we identify future research directions,including elucidating precise hydrocarbon pool(HCP)intermediates,optimizing zeolite structures through computational-guided design,and developing robust catalytic systems leveraging advanced characterization methods and artificial intelligence.By integrating multidisciplinary approaches from catalytic science,materials engineering,and reaction engineering,this review provides actionable guidance towards rational design and optimization of advanced catalytic systems for efficient methanol conversion processes.
