Electrochemical water splitting represents a sustainable technology for hydrogen(H_(2))production.However,its large-scale implementation is hindered by the high overpotentials required for both the cathodic hydrogen e...Electrochemical water splitting represents a sustainable technology for hydrogen(H_(2))production.However,its large-scale implementation is hindered by the high overpotentials required for both the cathodic hydrogen evolution reaction(HER)and the anodic oxygen evolution reaction(OER).Transition metal-based catalysts have garnered significant research interest as promising alternatives to noble-metal catalysts,owing to their low cost,tunable composition,and noble-metal-like catalytic activity.Nevertheless,systematic reviews on their application as bifunctional catalysts for overall water splitting(OWS)are still limited.This review comprehensively outlines the principal categories of bifunctional transition metal electrocatalysts derived from electrospun nanofibers(NFs),including metals,oxides,phosphides,sulfides,and carbides.Key strategies for enhancing their catalytic performance are systematically summarized,such as heterointerface engineering,heteroatom doping,metal-nonmetal-metal bridging architectures,and single-atom site design.Finally,current challenges and future research directions are discussed,aiming to provide insightful perspectives for the rational design of high-performance electrocatalysts for OWS.展开更多
Transition metal nitrides(TMNs)have been considered as promising alternative catalysts to noble metals in various electrocatalytic applications due to their noble metal-like electronic structures,high conductivity,low...Transition metal nitrides(TMNs)have been considered as promising alternative catalysts to noble metals in various electrocatalytic applications due to their noble metal-like electronic structures,high conductivity,low cost,as well as strong chemical stability,which could resist corrosion and oxidation in harsh operation conditions.Therefore,the rational design and controlled synthesis of TMNs with distinct structures play a vital role in developing highly efficient electrocatalysts toward electrochemical applications.This review provides a comprehensive summary of representative synthetic strategies for TMNs,such as direct nitridation,solidstate reaction,sol-gel assisted reaction,and wet-chemical reaction,presents the distinct structural characterizations,and demonstrates their advances in the electrochemical applications.Finally,we propose the remaining challenges and the future research directions on the exploration of TMNs with well-defined structures for electrocatalytic applications,which could shed light on the future development of high-performance electrocatalysts.展开更多
Peptides play important roles in chemistry,medicinal chemistry and life science,due to their high efficiency and specificity,unusual biological and therapeutic properties.As naturally occurring peptides often face wit...Peptides play important roles in chemistry,medicinal chemistry and life science,due to their high efficiency and specificity,unusual biological and therapeutic properties.As naturally occurring peptides often face with their intrinsic limitations including metabolic instability and low membrane permeability,the strategies for synthesizing unnatural amino acids and peptides are explored.Among the methods for modifying amino acids and peptides,chemo-and site-selective approaches are preferred because of the ability to fine-tuning structural features.Recently,transition metal-catalyzed Csingle bondH activation has been employed for the functionalization of amino acids and peptides.Through domino Csingle bondH activation/annulation,a series of structurally complex and diverse amino acids and peptides is constructed.This review highlights recent advances in the synthesis of unnatural amino acids and peptides via transition metal-catalyzed Csingle bondH activation/annulation.展开更多
The glass transition temperature(T_(g))of styrene-butadiene rubber(SBR)is a key parameter determining its low-temperature flexibility and processing performance.Accurate prediction of T_(g)is crucial formaterial desig...The glass transition temperature(T_(g))of styrene-butadiene rubber(SBR)is a key parameter determining its low-temperature flexibility and processing performance.Accurate prediction of T_(g)is crucial formaterial design and application optimisation.Addressing the limitations of traditional experimental measurements and theoretical models in terms of efficiency,cost,and accuracy,this study proposes a machine learning prediction framework that integrates multi-model ensemble and Bayesian optimization by constructing a multi-component feature dataset and algorithm optimization strategy.Based on the constructed high-quality dataset containing 96 SBR samples,ninemachine learning models were employed to predict the T_(g)of SBR and compare their prediction performance.Ultimately,aGPR-XGBoost mixed model was constructed through model ensemble,achieving high-precision prediction with R^(2)values greater than 0.9 on both the training and test sets.Further feature attribution and local effect analysis were conducted using feature analysis methods such as SHAP and ALE,revealing the nonlinear influence patterns of various components on T_(g),providing a theoretical basis for SBR formulation design and T_(g)regulation.The machine learning prediction framework established in this study combines high-precision prediction with interpretability,significantly enhancing the prediction performance of the T_(g)of SBR.It offers an efficient tool for SBR molecular design and holds great potential for promotion and application.展开更多
The volume change behavior of natural gas hydrate-bearing sediment is essential as it influences settlement,strength,and stiffness,which directly affect the stability of hydrate reservoirs during hydrate extraction or...The volume change behavior of natural gas hydrate-bearing sediment is essential as it influences settlement,strength,and stiffness,which directly affect the stability of hydrate reservoirs during hydrate extraction or in response to environmental changes.The volume change is influenced not only by stress but also by the formation and dissociation of hydrates.This study adopted a customized apparatus for one-dimensional compression tests,allowing independent control of gas pressure and effective stress.Tests were conducted on samples with different hydrate saturations along various temperature-gas pressure-effective stress paths,yielding some conclusions related to compressibility and creep.An unusual phenomenon was observed under low-stress conditions:hydrate formation led to shrinkage rather than expansion.Three potential mechanisms behind this occurrence were discussed.As hydrate saturation increases,the yield stress rises while the compression and swelling indexes remain minimally affected.After hydrate dissociation,the compression curve of hydrate-bearing sediment drops to that of hydrate-free sediment.Once hydrate is formed,the compression curve of hydrate-free sediment gradually approaches that of hydrate-bearing sediment during the subsequent loading.Under low-stress conditions,the creep of both hydrate-free and hydrate-bearing sediments is very weak.However,when stress increases,significantly beyond the yield stress,the creep of both sediments increases significantly,with hydrate-bearing sediment exhibiting much greater creep than hydrate-free sediment.展开更多
Marginal seas,as transitional zones,are closely connected to the open ocean and adjacent coastal systems.Their circulations often exhibit strong oscillatory behavior that shapes heat and salt transport,nutrient cyclin...Marginal seas,as transitional zones,are closely connected to the open ocean and adjacent coastal systems.Their circulations often exhibit strong oscillatory behavior that shapes heat and salt transport,nutrient cycling,and regional ocean-atmosphere interactions.However,the characteristics and underlying dynamics of these oscillations remain insufficiently understood.Using the unique three-layer alternating circulation in the South China Sea as an example,we show that the system undergoes a pronounced regime transition from 1993-2008 to 2009-2018.This transition is closely linked to the phase change of the Pacific Decadal Oscillation.Specifically,upper-layer cyclonic circulation intensifies during the pre-2009 but weakens during the post-2009 period,while the middle-layer anticyclonic circulation exhibits the opposite pattern.In contrast,the deep-layer circulation strengthens substantially during the post-20o9 period.These regime transitions arise from the interplay of surface wind forcing,the external exchanging current with the Pacific,and topographically modulated internal vertical coupling.The decadal trend of the upper-layer circulation is primarily wind-driven.The weakening of middle-layer circulation during pre-2oo9 is governed by pressure torque influenced by the upperlayer,whereas its post-2009 strengthening is attributed to vortex stretching associated with enhanced deep intrusion from the Pacific and a stronger deep-layer circulation.The findings clarify the oscillatory nature of South China Sea layered circulation under climate variability and highlight its role in regulating regional mass transport and ocean-atmosphere interaction.展开更多
The dissolvable polysulfides and sluggish Li_2S conversion kinetics are acknowledged as two significant challenges in the application lithium-sulfur(Li-S)batteries.Herein,we introduce a dual-doping strategy to modulat...The dissolvable polysulfides and sluggish Li_2S conversion kinetics are acknowledged as two significant challenges in the application lithium-sulfur(Li-S)batteries.Herein,we introduce a dual-doping strategy to modulate the electronic structure of MoS_(2),thereby obtaining a multifunctional catalyst that serves as an efficient sulfur host.The W/V dual single-atomdoped MoS_(2)grown on carbon nanofibers(CMWVS)demonstrates a strong adsorption ability for lithium polysulfides,suppressing the shuttle effects.Additionally,the doping process also results in the phase transition from 2H-MoS_(2)to 1T-MoS_(2)and generates sufficient edge sulfur atoms,promoting the charge/electron transfer and enriching the reaction sites.All these merits contribute to the superior conversion reaction kinetics,leading to the outstanding Li-S battery performance.When fabricated as cathodes by compositing with sulfur,the CMWVS/S cathode delivers a high capacity of 1481.7 mAh g^(-1)at 0.1 C(1 C=1672 mAh g^(-1))and maintains 816.3 m Ah g^(-1)after 1000 cycles at 1.0 C,indicating outstanding cycling stability.Even under a high sulfur loading of 7.9 mg cm^(-2)and lean electrolyte conditions(E/S ratio of 9.0μL mg^(-1)),the cathode achieves a high areal capacity of 8.2 m Ah cm^(-2),showing great promise for practical Li-S battery applications.This work broadens the scope of doping strategies in transition-metal dichalcogenides by tailoring their electronic structures,providing insightful direction for the rational development of high-efficiency electrocatalysts for advanced Li-S battery applications.展开更多
Conversion-type electrode materials hold significant promise for potassium-ion batteries(PIBs)due to their high theoretical capacities,yet their practical deployment is hindered by sluggish kinetics and irreversible s...Conversion-type electrode materials hold significant promise for potassium-ion batteries(PIBs)due to their high theoretical capacities,yet their practical deployment is hindered by sluggish kinetics and irreversible structural degradation.To overcome these limitations,we propose a rationally engineered nanoreactor architecture that stabilizes defect-rich MoS_(2)via interlayer incorporation of a carbon monolayer,followed by encapsulation within a nitrogen-doped carbon shell,forming a MoSSe@NC heterostructure.This tailored structure synergistically accelerates both K^(+)diffusion kinetics and electron transfer,enabling unprecedented rate performance(107 mAh g^(-1)at 10 Ag^(-1))and ultralong cyclability(86.5%capacity retention after 1200 cycles at 3 A g^(-1)).Mechanistic insights reveal a distinctive“adsorption-conversion”pathway,where sulfur vacancies on exposed S-Mo-S basal planes act as preferential K^(+)adsorption sites,effectively suppressing parasitic phase transitions during intercalation.In situ X-ray diffraction and transmission electron microscopy corroborate the structural reversibility of the conversion reaction,with the carbon matrix dynamically accommodating strain while preserving electrode integrity.This work not only advances the understanding of defect-driven interfacial chemistry in conversion-type materials but also provides a versatile strategy for designing high-performance anodes in next-generation PIBs through heterostructure engineering.展开更多
The Pliocene-Pleistocene transition(3.0-2.5 million years ago,Ma)was a critical period during which the Arctic ice sheets expanded extensively and intensified,with the establishment of a permanent ice sheet on Greenla...The Pliocene-Pleistocene transition(3.0-2.5 million years ago,Ma)was a critical period during which the Arctic ice sheets expanded extensively and intensified,with the establishment of a permanent ice sheet on Greenland marking the onset of a bipolar“icehouse”climate state.This interval,characterized by atmospheric CO_(2) concentrations between pre-industrial and modern levels(~280-400 ppmv),provides a critical time window for understanding ice-sheet response to external forcing.Using a high-resolution climate model and a 3D thermomechanical ice sheet model,we simulate the Greenland Ice Sheet(GrIS)volume evolution under different CO_(2) scenarios and analyze its periodic behavior during this period.Our results show that when the GrIS volume was small,its variability was strongly paced by 65°N summer insolation.As the ice sheet grew,its response shifted,becoming increasingly dominated by the obliquity cycle.The GrIS volume reconstruction,consistent with ice-rafted debris records,indicates that after approximately 2.7 Ma,the expanded GrIS exhibited enhanced suborbital to millennial-scale signals and greater ice dynamical variability-a pattern echoing the amplified millennial-scale climate events observed in late Quaternary Greenland ice cores.Furthermore,comparison with deep-sea oxygen isotope records shows that the GrIS began to significantly contribute to the 40,000-year cycle after 2.7 Ma,with its changes slightly leading the signal of the benthic δ^(18)O.This study clarifies the GrIS’s cyclic evolution and constrains its role in the climate system evolution during the Pliocene-Pleistocene transition.展开更多
Progressive skin fibrosis ultimately results in irreversible contractures,causing both joint dysfunction and cosmetic deformity.The key pathological features of skin fibrosis include persistent inflammation and abnorm...Progressive skin fibrosis ultimately results in irreversible contractures,causing both joint dysfunction and cosmetic deformity.The key pathological features of skin fibrosis include persistent inflammation and abnormal accumulation of the extracellular matrix(ECM),with epithelialmesenchymal transition(EMT)playing a critical role in disease progression.However,current therapeutic strategies for cutaneous fibrosis are largely palliative and often require repeated interventions,with limited efficacy.Celastrol(Cel)exerts anti-inflammatory and anti-fibrotic effects in skin tissue,but its clinical application is limited by poor bioavailability and a narrow therapeutic window.Tetrahedral framework nucleic acid(tFNA),a novel nanocarrier system,exhibits multiple advantages,including enhanced cellular uptake,improved cell viability,and intrinsic anti-fibrotic and anti-inflammatory properties.Therefore,this study applied tFNA-Cel complex(TCC)as an advanced nanotherapeutic agent,designed to exert a synergistic anti-fibrotic effect.In this study,an in vitro model of skin fibrosis was established using human keratinocyte(HaCaT)cells treated with 5 ng mL^(-1) transforming growth factor beta(TGF-β)for 24 h.The results showed that TCC significantly inhibited EMT progression by reducingα-smooth muscle actin(α-SMA)levels and increasing E-cadherin level.Compared to tFNA or Cel alone,TCC exhibited superior anti-fibrotic effects in the fibrosis model,as evidenced by modulation of SMAD family member 2(SMAD2)signaling and collagen I expression.Furthermore,the TCC group showed lower levels of nuclear factorκB p65(NF-κB p65),BCL-2-associated X protein(Bax),and reactive oxygen species(ROS)compared to the Cel or tFNA groups.These findings highlight TCC as a promising treatment for skin fibrosis,with its synergistic anti-fibrotic effects providing new therapeutic avenues.展开更多
The moment a media delegation from the Republic of the Congo arrived at the Othello Kitchenware Museum on 18 November 2025,they were greeted with a vivid show of Guangdong’s industrial strength.Standing before them w...The moment a media delegation from the Republic of the Congo arrived at the Othello Kitchenware Museum on 18 November 2025,they were greeted with a vivid show of Guangdong’s industrial strength.Standing before them was not a typical exhibition hall,but a building shaped like a gleaming stainless-steel cooking pot.展开更多
Water molecules can form hydrogen bonds.At the solid surfaces,the preferential alignment of water molecules due to the heterogeneous atomic distributions can induce ordered hydrogen bond networks of water molecules wi...Water molecules can form hydrogen bonds.At the solid surfaces,the preferential alignment of water molecules due to the heterogeneous atomic distributions can induce ordered hydrogen bond networks of water molecules with spatially heterogeneous patterns and slower dynamics compared to bulk water.Both the confinement and the surface atomic structures can induce the water phase transitions at low dimensional spaces.Here,we review how the phase transitions of interfacial water affect the surface physical behaviors,such as wetting,ice nucleation and the terahertz-wave-water interactions,from solid materials to the biological surfaces.These works help extend our knowledge of the physics properties of the interfacial water,particularly the multi-phase behaviors in materials and biology sciences.展开更多
Controllable photoreaction transition of photosensitizers(PSs)provides a highly promising approach for achieving efficient photodynamic therapy(PDT).However,tumor microenvironment-triggered phototransition remains a s...Controllable photoreaction transition of photosensitizers(PSs)provides a highly promising approach for achieving efficient photodynamic therapy(PDT).However,tumor microenvironment-triggered phototransition remains a significant challenge and has not yet been reported.In this work,we develop a hydrogen bond self-assembly(HBSA)strategy that is triggered by the acidic tumor microenvironment to enable the photodynamic transition of tetra(4-carboxylphenyl)porphyrin(TCPP)PSs from type Ⅱ to type Ⅰ reactions.Upon self-assembly of TCPP monomers into TCPP assemblies(TCPP-ass),the generated reactive oxygen species shift from singlet oxygen to superoxide anions,which induces caspase-3/GSDME-mediated programmed pyroptosis,enabling rapid and complete solid tumor elimination with minimized adverse effects and enhanced therapeutic efficacy.Crucially,the HBSA process occurs exclusively within tumor cells,and this tumor-specific self-assembly strategy not only utilizes high tissue penetration of TCPP molecular-PSs,but also avoids phototoxicity caused by the formation and accumulation of TCPP-ass nano-PSs in normal tissue,providing an innovative approach for precise cancer therapy.展开更多
AIM:To determine whether paeonol(Pae),a naturally occurring phenolic compound,can serve as an effective pharmacological inhibitor of posterior capsular opacification(PCO).METHODS:A rat model of cataract surgery—induc...AIM:To determine whether paeonol(Pae),a naturally occurring phenolic compound,can serve as an effective pharmacological inhibitor of posterior capsular opacification(PCO).METHODS:A rat model of cataract surgery—induced PCO was established,and Pae was administered via anterior chamber injection to evaluate its preventive effect on capsular opacification and fibrotic remodeling.Histological and immunohistochemical analyses were performed to assess epithelial-mesenchymal transition(EMT)—related changes in lens epithelial cells(LECs).Ex vivo lens capsule cultures were employed to examine the expression of Vimentin and Zonula Occludens-1(ZO-1)by immunofluorescence and immunohistochemistry.In the human LEC line SRA01/04,EMT marker expression at both mRNA and protein levels was analyzed following transforming growth factor beta 2(TGF-β2)stimulation,with Pae treatment.Western blotting and immunofluorescence were used to investigate the effect of Pae on TGF-β/Smad signaling and AMP-activated protein kinase(AMPK)activation.Molecular docking was performed to predict Pae–AMPK binding,and rescue experiments with AMPK inhibition were conducted to validate the mechanistic pathway.RESULTS:Pae significantly reduced capsular opacification and fibrotic remodeling in the rat PCO model compared with controls.In LECs,Pae markedly suppressed TGF-β2–induced EMT,evidenced by decreased expression of mesenchymal markers,such as Vimentin,Fibronectin,Collagen 1A1,α-SMA and preserved epithelial junctional protein ZO-1.Mechanistically,Pae was predicted to directly interact with the catalytic pocket of AMPK,which was experimentally confirmed by enhanced AMPK phosphorylation and nuclear translocation(P<0.05).This activation disrupted canonical TGF-β/Smad signaling,leading to suppression of EMT.Rescue experiments using AMPK inhibition abrogated the anti-EMT effect of Pae,further validating the AMPK-dependent mechanism.CONCLUSION:Pae exerts a potent inhibitory effect on PCO formation by blocking EMT of LECs through direct activation of AMPK and subsequent disruption of TGF-β/Smad signaling.展开更多
During the oxygen evolution reaction(OER),reconstruction of transition metal sulfides(TMSs)is inevitable.However,the lack of a clear theoretical understanding of this process has impeded the development of effective r...During the oxygen evolution reaction(OER),reconstruction of transition metal sulfides(TMSs)is inevitable.However,the lack of a clear theoretical understanding of this process has impeded the development of effective reconstruction regulation strategies.In this study,we first explored the reconstruction mechanism of CoS_(2)during OER from the perspective of electronic structure and identified two possible pathways:the OH-assisted mechanism and the O-assisted mechanism.Further verification showed that these mechanisms are universally applicable to other TMSs(e.g.,FeS_(2)).Based on the reconstruction mechanism,we investigated the basic reasons for the influence of various regulation strategies,such as vacancy modification and facet engineering,on the reconstruction ability.This verified that the method of analyzing the change in the reconstruction ability of catalysts based on the reconstruction mechanism has a high degree of applicability.Importantly,we proposed a core regulation strategy:the coordination symmetry regulation strategy.Specifically,by breaking the symmetry of the surface coordination environment of TMSs(such as introducing heteroatom doping or strain),the reconstruction process will be facilitated.Our findings provide a comprehensive mechanistic explanation for the reconstruction of TMS catalysts and offer a new idea for the rational design of OER catalysts with controllable reconstruction capacity.展开更多
Conventional Tb^(3+)-doped phosphors typically suffer from concentration quenching once the doping level exceeds a critical threshold.Consequently,the development of Tb^(3+)phosphors with intrinsic resistance to conce...Conventional Tb^(3+)-doped phosphors typically suffer from concentration quenching once the doping level exceeds a critical threshold.Consequently,the development of Tb^(3+)phosphors with intrinsic resistance to concentration quenching has become a key research focus.In this work,we successfully synthesized KBi(MoO_(4))_(2):x Tb^(3+)(x=0-100 at%)(denoted as KBM:x Tb^(3+))phosphors via a high-temperature solid-state reaction.Remarkably,no concentration quenching was observed across the entire doping range.This anti-quenching behavior originates from the large Tb^(3+)-Tb^(3+)interionic distance(>5Å)inherent to the quasi-layered crystal structure,which effectively suppresses multipole-interaction-mediated energy migration.At full Tb^(3+)substitution(x=100 at%),the material undergoes a structural phase transition from the monoclinic KBM phase to the triclinicα-KTb(MoO_(4))_(2)(α-KTM)phase.Theα-KTM phosphor exhibits excellent thermal stability(activation energy=0.6129 eV)and a single-exponential decay profile,whereas KBM:x Tb^(3+)(x<100%)display double-exponential decay behaviors,attributed to dual energy transfer pathways.These findings provide new insights into the luminescence mechanisms of high-concentration rare-earth-doped systems and offer guidance for designing nextgeneration anti-quenching phosphors.展开更多
In Chin.Phys.B 34114704(2025),Eq.(7)and the associated unit notation were incorrect.The correct ones are present here.Since Eq.(7)is an in-built expression in the simulation package,the correction is purely typographi...In Chin.Phys.B 34114704(2025),Eq.(7)and the associated unit notation were incorrect.The correct ones are present here.Since Eq.(7)is an in-built expression in the simulation package,the correction is purely typographical and does not affect the simulation procedure,numerical results,or the conclusions.展开更多
Rapid regional population shifts and spatial polarization have heightened pressure on cultivated land—a critical resource demanding urgent attention amid ongoing urban-rural transition.This study selects Jiangsu prov...Rapid regional population shifts and spatial polarization have heightened pressure on cultivated land—a critical resource demanding urgent attention amid ongoing urban-rural transition.This study selects Jiangsu province,a national leader in both economic and agricultural development,as a case area to construct a multidimensional framework for assessing the recessive morphological characteristics of multifunctional cultivated land use.We examine temporal dynamics,spatial heterogeneity,and propose an integrated zoning strategy based on empirical analysis.The results reveal that:(1)The recessive morphology index shows a consistent upward trend,with structural breaks in 2007 and 2013,and a spatial shift from“higher in the east and lower in the west”to“higher in the south and lower in the north.”(2)Coordination among sub-dimensions of the index has steadily improved.(3)The index is expected to continue rising in the next decade,though at a slower pace.(4)To promote coordinated multidimensional land-use development,we recommend a policy framework that reinforces existing strengths,addresses weaknesses,and adapts zoning schemes to current spatial conditions.This research offers new insights into multifunctional cultivated land systems and underscores their role in enhancing human well-being,securing food supply,and supporting sustainable urban-rural integration.展开更多
基金Supported by the National Natural Science Foundation of China(No.52273056)the Science and Technology Development Program of Jilin Province,China(No.YDZJ202501ZYTS305)。
文摘Electrochemical water splitting represents a sustainable technology for hydrogen(H_(2))production.However,its large-scale implementation is hindered by the high overpotentials required for both the cathodic hydrogen evolution reaction(HER)and the anodic oxygen evolution reaction(OER).Transition metal-based catalysts have garnered significant research interest as promising alternatives to noble-metal catalysts,owing to their low cost,tunable composition,and noble-metal-like catalytic activity.Nevertheless,systematic reviews on their application as bifunctional catalysts for overall water splitting(OWS)are still limited.This review comprehensively outlines the principal categories of bifunctional transition metal electrocatalysts derived from electrospun nanofibers(NFs),including metals,oxides,phosphides,sulfides,and carbides.Key strategies for enhancing their catalytic performance are systematically summarized,such as heterointerface engineering,heteroatom doping,metal-nonmetal-metal bridging architectures,and single-atom site design.Finally,current challenges and future research directions are discussed,aiming to provide insightful perspectives for the rational design of high-performance electrocatalysts for OWS.
基金supported by the National Natural Science Foundation of China(52471219 and 92463305)State Key Laboratory of New Ceramic Materials Tsinghua University(KFZD202402)Fundamental Research Funds for the Central Universities(00007838)。
文摘Transition metal nitrides(TMNs)have been considered as promising alternative catalysts to noble metals in various electrocatalytic applications due to their noble metal-like electronic structures,high conductivity,low cost,as well as strong chemical stability,which could resist corrosion and oxidation in harsh operation conditions.Therefore,the rational design and controlled synthesis of TMNs with distinct structures play a vital role in developing highly efficient electrocatalysts toward electrochemical applications.This review provides a comprehensive summary of representative synthetic strategies for TMNs,such as direct nitridation,solidstate reaction,sol-gel assisted reaction,and wet-chemical reaction,presents the distinct structural characterizations,and demonstrates their advances in the electrochemical applications.Finally,we propose the remaining challenges and the future research directions on the exploration of TMNs with well-defined structures for electrocatalytic applications,which could shed light on the future development of high-performance electrocatalysts.
基金supported by the Natural Science Foundation of Jiangsu Province(No.BK20220409)the National Natural Science Foundation of China(No.22401153)+2 种基金the FWO[Fund for Scientific Research-Flanders(Belgium)]for financial support(recipient Erik V.Van der Eycken)the Research Council of the KU Leuven(recipient Erik V.Van der Eycken)the support of the"RUDN University Strategic Academic Leadership Program"(recipient Erik V.Van der Eycken).
文摘Peptides play important roles in chemistry,medicinal chemistry and life science,due to their high efficiency and specificity,unusual biological and therapeutic properties.As naturally occurring peptides often face with their intrinsic limitations including metabolic instability and low membrane permeability,the strategies for synthesizing unnatural amino acids and peptides are explored.Among the methods for modifying amino acids and peptides,chemo-and site-selective approaches are preferred because of the ability to fine-tuning structural features.Recently,transition metal-catalyzed Csingle bondH activation has been employed for the functionalization of amino acids and peptides.Through domino Csingle bondH activation/annulation,a series of structurally complex and diverse amino acids and peptides is constructed.This review highlights recent advances in the synthesis of unnatural amino acids and peptides via transition metal-catalyzed Csingle bondH activation/annulation.
基金supported by the National Natural Science Foundation of China(grant numbers 52250357 and 52203003).
文摘The glass transition temperature(T_(g))of styrene-butadiene rubber(SBR)is a key parameter determining its low-temperature flexibility and processing performance.Accurate prediction of T_(g)is crucial formaterial design and application optimisation.Addressing the limitations of traditional experimental measurements and theoretical models in terms of efficiency,cost,and accuracy,this study proposes a machine learning prediction framework that integrates multi-model ensemble and Bayesian optimization by constructing a multi-component feature dataset and algorithm optimization strategy.Based on the constructed high-quality dataset containing 96 SBR samples,ninemachine learning models were employed to predict the T_(g)of SBR and compare their prediction performance.Ultimately,aGPR-XGBoost mixed model was constructed through model ensemble,achieving high-precision prediction with R^(2)values greater than 0.9 on both the training and test sets.Further feature attribution and local effect analysis were conducted using feature analysis methods such as SHAP and ALE,revealing the nonlinear influence patterns of various components on T_(g),providing a theoretical basis for SBR formulation design and T_(g)regulation.The machine learning prediction framework established in this study combines high-precision prediction with interpretability,significantly enhancing the prediction performance of the T_(g)of SBR.It offers an efficient tool for SBR molecular design and holds great potential for promotion and application.
基金supported by the National Natural Science Foundation of China(Grant No.42171135)the Science and Technology Program of CNOOC Research Institute(Grant No.2023OTKK03)the“CUG Scholar”Scientific Research Funds at China University of Geosciences(Project No.2022098).
文摘The volume change behavior of natural gas hydrate-bearing sediment is essential as it influences settlement,strength,and stiffness,which directly affect the stability of hydrate reservoirs during hydrate extraction or in response to environmental changes.The volume change is influenced not only by stress but also by the formation and dissociation of hydrates.This study adopted a customized apparatus for one-dimensional compression tests,allowing independent control of gas pressure and effective stress.Tests were conducted on samples with different hydrate saturations along various temperature-gas pressure-effective stress paths,yielding some conclusions related to compressibility and creep.An unusual phenomenon was observed under low-stress conditions:hydrate formation led to shrinkage rather than expansion.Three potential mechanisms behind this occurrence were discussed.As hydrate saturation increases,the yield stress rises while the compression and swelling indexes remain minimally affected.After hydrate dissociation,the compression curve of hydrate-bearing sediment drops to that of hydrate-free sediment.Once hydrate is formed,the compression curve of hydrate-free sediment gradually approaches that of hydrate-bearing sediment during the subsequent loading.Under low-stress conditions,the creep of both hydrate-free and hydrate-bearing sediments is very weak.However,when stress increases,significantly beyond the yield stress,the creep of both sediments increases significantly,with hydrate-bearing sediment exhibiting much greater creep than hydrate-free sediment.
基金supported by the National Natural Science Foundation of China(42376024and 42450181)the Science and Technology Development Fund,Macao SAR(File/Project no.001/2024/SKL)+2 种基金supported by the Centre for Regional Oceans in the University of Macao(SP2025-00005-CRO)CORE,which is a joint research center for ocean research between Laoshan Laboratory and HKUSTsubstantially supported by a grant from the Research Grants Council of the Hong Kong Special Administrative Region,China(AoE/P-601/23-N and GRF 16310724).
文摘Marginal seas,as transitional zones,are closely connected to the open ocean and adjacent coastal systems.Their circulations often exhibit strong oscillatory behavior that shapes heat and salt transport,nutrient cycling,and regional ocean-atmosphere interactions.However,the characteristics and underlying dynamics of these oscillations remain insufficiently understood.Using the unique three-layer alternating circulation in the South China Sea as an example,we show that the system undergoes a pronounced regime transition from 1993-2008 to 2009-2018.This transition is closely linked to the phase change of the Pacific Decadal Oscillation.Specifically,upper-layer cyclonic circulation intensifies during the pre-2009 but weakens during the post-2009 period,while the middle-layer anticyclonic circulation exhibits the opposite pattern.In contrast,the deep-layer circulation strengthens substantially during the post-20o9 period.These regime transitions arise from the interplay of surface wind forcing,the external exchanging current with the Pacific,and topographically modulated internal vertical coupling.The decadal trend of the upper-layer circulation is primarily wind-driven.The weakening of middle-layer circulation during pre-2oo9 is governed by pressure torque influenced by the upperlayer,whereas its post-2009 strengthening is attributed to vortex stretching associated with enhanced deep intrusion from the Pacific and a stronger deep-layer circulation.The findings clarify the oscillatory nature of South China Sea layered circulation under climate variability and highlight its role in regulating regional mass transport and ocean-atmosphere interaction.
基金supported by the National Natural Science Foundation of China(52402166)the Science and Technology Development Fund+2 种基金Macao SAR(0065/2023/AFJ,0116/2022/A3)the Australian Research Council(DE220100154)the Natural Science Foundation of Guangdong Province(2025A1515011120)。
文摘The dissolvable polysulfides and sluggish Li_2S conversion kinetics are acknowledged as two significant challenges in the application lithium-sulfur(Li-S)batteries.Herein,we introduce a dual-doping strategy to modulate the electronic structure of MoS_(2),thereby obtaining a multifunctional catalyst that serves as an efficient sulfur host.The W/V dual single-atomdoped MoS_(2)grown on carbon nanofibers(CMWVS)demonstrates a strong adsorption ability for lithium polysulfides,suppressing the shuttle effects.Additionally,the doping process also results in the phase transition from 2H-MoS_(2)to 1T-MoS_(2)and generates sufficient edge sulfur atoms,promoting the charge/electron transfer and enriching the reaction sites.All these merits contribute to the superior conversion reaction kinetics,leading to the outstanding Li-S battery performance.When fabricated as cathodes by compositing with sulfur,the CMWVS/S cathode delivers a high capacity of 1481.7 mAh g^(-1)at 0.1 C(1 C=1672 mAh g^(-1))and maintains 816.3 m Ah g^(-1)after 1000 cycles at 1.0 C,indicating outstanding cycling stability.Even under a high sulfur loading of 7.9 mg cm^(-2)and lean electrolyte conditions(E/S ratio of 9.0μL mg^(-1)),the cathode achieves a high areal capacity of 8.2 m Ah cm^(-2),showing great promise for practical Li-S battery applications.This work broadens the scope of doping strategies in transition-metal dichalcogenides by tailoring their electronic structures,providing insightful direction for the rational development of high-efficiency electrocatalysts for advanced Li-S battery applications.
基金financially supported by the supported by Shandong Provincial Natural Science Foundation(ZR2024MB108)Taishan Young Scholar Program(tsqn202312312)Excellent Young Scholars of the Shandong Provincial Natural Science Foundation(Overseas)(2023HWYQ-112)。
文摘Conversion-type electrode materials hold significant promise for potassium-ion batteries(PIBs)due to their high theoretical capacities,yet their practical deployment is hindered by sluggish kinetics and irreversible structural degradation.To overcome these limitations,we propose a rationally engineered nanoreactor architecture that stabilizes defect-rich MoS_(2)via interlayer incorporation of a carbon monolayer,followed by encapsulation within a nitrogen-doped carbon shell,forming a MoSSe@NC heterostructure.This tailored structure synergistically accelerates both K^(+)diffusion kinetics and electron transfer,enabling unprecedented rate performance(107 mAh g^(-1)at 10 Ag^(-1))and ultralong cyclability(86.5%capacity retention after 1200 cycles at 3 A g^(-1)).Mechanistic insights reveal a distinctive“adsorption-conversion”pathway,where sulfur vacancies on exposed S-Mo-S basal planes act as preferential K^(+)adsorption sites,effectively suppressing parasitic phase transitions during intercalation.In situ X-ray diffraction and transmission electron microscopy corroborate the structural reversibility of the conversion reaction,with the carbon matrix dynamically accommodating strain while preserving electrode integrity.This work not only advances the understanding of defect-driven interfacial chemistry in conversion-type materials but also provides a versatile strategy for designing high-performance anodes in next-generation PIBs through heterostructure engineering.
基金funded by the Strategy Priority Research Program(Category B)of the Chinese Academy of Sciences(Grant No.XDB0710000)the National Key Research and Development Program(No.2022YFF0801504)+1 种基金the National Natural Science Foundation of China(Nos.42488201,41907371)support from the IGGCAS Key Program(No.IGGCAS-202201).
文摘The Pliocene-Pleistocene transition(3.0-2.5 million years ago,Ma)was a critical period during which the Arctic ice sheets expanded extensively and intensified,with the establishment of a permanent ice sheet on Greenland marking the onset of a bipolar“icehouse”climate state.This interval,characterized by atmospheric CO_(2) concentrations between pre-industrial and modern levels(~280-400 ppmv),provides a critical time window for understanding ice-sheet response to external forcing.Using a high-resolution climate model and a 3D thermomechanical ice sheet model,we simulate the Greenland Ice Sheet(GrIS)volume evolution under different CO_(2) scenarios and analyze its periodic behavior during this period.Our results show that when the GrIS volume was small,its variability was strongly paced by 65°N summer insolation.As the ice sheet grew,its response shifted,becoming increasingly dominated by the obliquity cycle.The GrIS volume reconstruction,consistent with ice-rafted debris records,indicates that after approximately 2.7 Ma,the expanded GrIS exhibited enhanced suborbital to millennial-scale signals and greater ice dynamical variability-a pattern echoing the amplified millennial-scale climate events observed in late Quaternary Greenland ice cores.Furthermore,comparison with deep-sea oxygen isotope records shows that the GrIS began to significantly contribute to the 40,000-year cycle after 2.7 Ma,with its changes slightly leading the signal of the benthic δ^(18)O.This study clarifies the GrIS’s cyclic evolution and constrains its role in the climate system evolution during the Pliocene-Pleistocene transition.
基金supported by the National Natural Science Foundation of China(82101077)Sichuan Science and Technology Program(2023NSFSC1516)+2 种基金West China School/Hospital of Stomatology Sichuan University(RCDWJS2023-5)Fundamental Research Funds for the Central UniversitiesResearch and Develop Program,West China School/Hospital of Stomatology Sichuan University。
文摘Progressive skin fibrosis ultimately results in irreversible contractures,causing both joint dysfunction and cosmetic deformity.The key pathological features of skin fibrosis include persistent inflammation and abnormal accumulation of the extracellular matrix(ECM),with epithelialmesenchymal transition(EMT)playing a critical role in disease progression.However,current therapeutic strategies for cutaneous fibrosis are largely palliative and often require repeated interventions,with limited efficacy.Celastrol(Cel)exerts anti-inflammatory and anti-fibrotic effects in skin tissue,but its clinical application is limited by poor bioavailability and a narrow therapeutic window.Tetrahedral framework nucleic acid(tFNA),a novel nanocarrier system,exhibits multiple advantages,including enhanced cellular uptake,improved cell viability,and intrinsic anti-fibrotic and anti-inflammatory properties.Therefore,this study applied tFNA-Cel complex(TCC)as an advanced nanotherapeutic agent,designed to exert a synergistic anti-fibrotic effect.In this study,an in vitro model of skin fibrosis was established using human keratinocyte(HaCaT)cells treated with 5 ng mL^(-1) transforming growth factor beta(TGF-β)for 24 h.The results showed that TCC significantly inhibited EMT progression by reducingα-smooth muscle actin(α-SMA)levels and increasing E-cadherin level.Compared to tFNA or Cel alone,TCC exhibited superior anti-fibrotic effects in the fibrosis model,as evidenced by modulation of SMAD family member 2(SMAD2)signaling and collagen I expression.Furthermore,the TCC group showed lower levels of nuclear factorκB p65(NF-κB p65),BCL-2-associated X protein(Bax),and reactive oxygen species(ROS)compared to the Cel or tFNA groups.These findings highlight TCC as a promising treatment for skin fibrosis,with its synergistic anti-fibrotic effects providing new therapeutic avenues.
文摘The moment a media delegation from the Republic of the Congo arrived at the Othello Kitchenware Museum on 18 November 2025,they were greeted with a vivid show of Guangdong’s industrial strength.Standing before them was not a typical exhibition hall,but a building shaped like a gleaming stainless-steel cooking pot.
基金supported by the National Natural Science Foundation of China(Grant Nos.22576126,12074394,12022508).
文摘Water molecules can form hydrogen bonds.At the solid surfaces,the preferential alignment of water molecules due to the heterogeneous atomic distributions can induce ordered hydrogen bond networks of water molecules with spatially heterogeneous patterns and slower dynamics compared to bulk water.Both the confinement and the surface atomic structures can induce the water phase transitions at low dimensional spaces.Here,we review how the phase transitions of interfacial water affect the surface physical behaviors,such as wetting,ice nucleation and the terahertz-wave-water interactions,from solid materials to the biological surfaces.These works help extend our knowledge of the physics properties of the interfacial water,particularly the multi-phase behaviors in materials and biology sciences.
基金supported by the National Natural Science Foundation of China(22176058)the Science and Technology Commission of Shanghai Municipality(24DX1400200,23ZR1416100,25ZR1401082)+1 种基金the Program of Introducing Talents of Discipline to Universities(B16017)the Fundamental Research Funds for the Central Universities(222201717003)。
文摘Controllable photoreaction transition of photosensitizers(PSs)provides a highly promising approach for achieving efficient photodynamic therapy(PDT).However,tumor microenvironment-triggered phototransition remains a significant challenge and has not yet been reported.In this work,we develop a hydrogen bond self-assembly(HBSA)strategy that is triggered by the acidic tumor microenvironment to enable the photodynamic transition of tetra(4-carboxylphenyl)porphyrin(TCPP)PSs from type Ⅱ to type Ⅰ reactions.Upon self-assembly of TCPP monomers into TCPP assemblies(TCPP-ass),the generated reactive oxygen species shift from singlet oxygen to superoxide anions,which induces caspase-3/GSDME-mediated programmed pyroptosis,enabling rapid and complete solid tumor elimination with minimized adverse effects and enhanced therapeutic efficacy.Crucially,the HBSA process occurs exclusively within tumor cells,and this tumor-specific self-assembly strategy not only utilizes high tissue penetration of TCPP molecular-PSs,but also avoids phototoxicity caused by the formation and accumulation of TCPP-ass nano-PSs in normal tissue,providing an innovative approach for precise cancer therapy.
基金Supported by the Projects of Medical and Health Technology Development Program in Shandong Province(No.202107021009)Shandong Provincial Traditional Chinese Medicine Science and Technology Project(No.M-2023118).
文摘AIM:To determine whether paeonol(Pae),a naturally occurring phenolic compound,can serve as an effective pharmacological inhibitor of posterior capsular opacification(PCO).METHODS:A rat model of cataract surgery—induced PCO was established,and Pae was administered via anterior chamber injection to evaluate its preventive effect on capsular opacification and fibrotic remodeling.Histological and immunohistochemical analyses were performed to assess epithelial-mesenchymal transition(EMT)—related changes in lens epithelial cells(LECs).Ex vivo lens capsule cultures were employed to examine the expression of Vimentin and Zonula Occludens-1(ZO-1)by immunofluorescence and immunohistochemistry.In the human LEC line SRA01/04,EMT marker expression at both mRNA and protein levels was analyzed following transforming growth factor beta 2(TGF-β2)stimulation,with Pae treatment.Western blotting and immunofluorescence were used to investigate the effect of Pae on TGF-β/Smad signaling and AMP-activated protein kinase(AMPK)activation.Molecular docking was performed to predict Pae–AMPK binding,and rescue experiments with AMPK inhibition were conducted to validate the mechanistic pathway.RESULTS:Pae significantly reduced capsular opacification and fibrotic remodeling in the rat PCO model compared with controls.In LECs,Pae markedly suppressed TGF-β2–induced EMT,evidenced by decreased expression of mesenchymal markers,such as Vimentin,Fibronectin,Collagen 1A1,α-SMA and preserved epithelial junctional protein ZO-1.Mechanistically,Pae was predicted to directly interact with the catalytic pocket of AMPK,which was experimentally confirmed by enhanced AMPK phosphorylation and nuclear translocation(P<0.05).This activation disrupted canonical TGF-β/Smad signaling,leading to suppression of EMT.Rescue experiments using AMPK inhibition abrogated the anti-EMT effect of Pae,further validating the AMPK-dependent mechanism.CONCLUSION:Pae exerts a potent inhibitory effect on PCO formation by blocking EMT of LECs through direct activation of AMPK and subsequent disruption of TGF-β/Smad signaling.
基金supported by the National Key Research and Development program(2022YFA1504000)the National Natural Science Foundation of China(22302101)+4 种基金the Fundamental Research Funds for the Central Universities(63185015)the Shenzhen Science and Technology Program(JCYJ20210324121002007,JCYJ20230807151503007)the Yunnan Provincial Science and Technology Project at Southwest United Graduate School(202402AO370001)the China Postdoctoral Science Foundation(2022M721699)the Guangdong Basic and Applied Basic Research Foundation(2024A1515010347).
文摘During the oxygen evolution reaction(OER),reconstruction of transition metal sulfides(TMSs)is inevitable.However,the lack of a clear theoretical understanding of this process has impeded the development of effective reconstruction regulation strategies.In this study,we first explored the reconstruction mechanism of CoS_(2)during OER from the perspective of electronic structure and identified two possible pathways:the OH-assisted mechanism and the O-assisted mechanism.Further verification showed that these mechanisms are universally applicable to other TMSs(e.g.,FeS_(2)).Based on the reconstruction mechanism,we investigated the basic reasons for the influence of various regulation strategies,such as vacancy modification and facet engineering,on the reconstruction ability.This verified that the method of analyzing the change in the reconstruction ability of catalysts based on the reconstruction mechanism has a high degree of applicability.Importantly,we proposed a core regulation strategy:the coordination symmetry regulation strategy.Specifically,by breaking the symmetry of the surface coordination environment of TMSs(such as introducing heteroatom doping or strain),the reconstruction process will be facilitated.Our findings provide a comprehensive mechanistic explanation for the reconstruction of TMS catalysts and offer a new idea for the rational design of OER catalysts with controllable reconstruction capacity.
基金supported by the Natural Science Research Project of Anhui Province Education Department for Excellent Young Scholars(Grant No.2024AH030007)the National Natural Science Foundation of China(Grant No.52202001)。
文摘Conventional Tb^(3+)-doped phosphors typically suffer from concentration quenching once the doping level exceeds a critical threshold.Consequently,the development of Tb^(3+)phosphors with intrinsic resistance to concentration quenching has become a key research focus.In this work,we successfully synthesized KBi(MoO_(4))_(2):x Tb^(3+)(x=0-100 at%)(denoted as KBM:x Tb^(3+))phosphors via a high-temperature solid-state reaction.Remarkably,no concentration quenching was observed across the entire doping range.This anti-quenching behavior originates from the large Tb^(3+)-Tb^(3+)interionic distance(>5Å)inherent to the quasi-layered crystal structure,which effectively suppresses multipole-interaction-mediated energy migration.At full Tb^(3+)substitution(x=100 at%),the material undergoes a structural phase transition from the monoclinic KBM phase to the triclinicα-KTb(MoO_(4))_(2)(α-KTM)phase.Theα-KTM phosphor exhibits excellent thermal stability(activation energy=0.6129 eV)and a single-exponential decay profile,whereas KBM:x Tb^(3+)(x<100%)display double-exponential decay behaviors,attributed to dual energy transfer pathways.These findings provide new insights into the luminescence mechanisms of high-concentration rare-earth-doped systems and offer guidance for designing nextgeneration anti-quenching phosphors.
文摘In Chin.Phys.B 34114704(2025),Eq.(7)and the associated unit notation were incorrect.The correct ones are present here.Since Eq.(7)is an in-built expression in the simulation package,the correction is purely typographical and does not affect the simulation procedure,numerical results,or the conclusions.
基金National Natural Science Foundation of China,No.42101252。
文摘Rapid regional population shifts and spatial polarization have heightened pressure on cultivated land—a critical resource demanding urgent attention amid ongoing urban-rural transition.This study selects Jiangsu province,a national leader in both economic and agricultural development,as a case area to construct a multidimensional framework for assessing the recessive morphological characteristics of multifunctional cultivated land use.We examine temporal dynamics,spatial heterogeneity,and propose an integrated zoning strategy based on empirical analysis.The results reveal that:(1)The recessive morphology index shows a consistent upward trend,with structural breaks in 2007 and 2013,and a spatial shift from“higher in the east and lower in the west”to“higher in the south and lower in the north.”(2)Coordination among sub-dimensions of the index has steadily improved.(3)The index is expected to continue rising in the next decade,though at a slower pace.(4)To promote coordinated multidimensional land-use development,we recommend a policy framework that reinforces existing strengths,addresses weaknesses,and adapts zoning schemes to current spatial conditions.This research offers new insights into multifunctional cultivated land systems and underscores their role in enhancing human well-being,securing food supply,and supporting sustainable urban-rural integration.
