Three photosystem I(PSⅠ)particles associated with different amounts of light-harvesting complex I(LHCI)were isolated from a phycocyanin 645(PC645)-containing cryptophyte Chroomonas placoidea by Triton X-100 sucrose g...Three photosystem I(PSⅠ)particles associated with different amounts of light-harvesting complex I(LHCI)were isolated from a phycocyanin 645(PC645)-containing cryptophyte Chroomonas placoidea by Triton X-100 sucrose gradient centrifugation.Two active PSⅠ-LHCⅠparticles(Bands 4 and 5)were resolved from thylakoids stripped of cations only,which implied that LHC migration and the adjustment of energy distribution between photosystemⅡ(PSⅡ)and PSⅠfacilitated by cations could also occur in cryptophytes,like in higher plants.Peptide analysis revealed that 19.8-,10-,and 8.3-kDa peptides corresponding toβ,α1,andα2 subunits of PC645,respectively,were present in Bands 4 and 5.Analyses of fluorescence and circular dichroism spectra and Gauss analyses revealed efficient energy couplings between PC645 and chlorophyll within both of these PSⅠ-LHCⅠparticles.The excitation energy absorbed by PC645 could be directly transferred to chlorophyll a in the PSⅠcore or via the chlorophyll a/c-protein complex of LHCⅠ.Based on these observations,we designated the two PSⅠ-LHCⅠparticles as phycocyanin-PSⅠcomplexes,which have not been reported previously.Band 4-2 was a sub-complex of Band 4 and was almost depleted of LHCⅠ(the chlorophyll a/c-protein complex was designated as Band 4-1)and PC645.Therefore,Band 4-2 was recognized as the PSⅠcore complex.Negative staining and transmission electron microscopy images of Band 4 gave a direct view that the PC645 component attached with chlorophyll-protein complexes in a regular structure as hollow ring shape.Furthermore,while previous studies have indicated that PC645 associates with PSⅡ,our results reveal that,in this cryptophytic alga,PC645 exhibits structural—but not preferential—association with PSⅠ,which provided new information about the architecture and function of the energy transfer system comprising phycobiliproteins and chlorophyll-protein complexes in cryptophytes.展开更多
Complex renal calculi,including staghorn and multiple renal stones,remain a significantchallenge in urological practice.The lifetime prevalence of urolithiasis ranges from approximately 5%–15%worldwide has clearly in...Complex renal calculi,including staghorn and multiple renal stones,remain a significantchallenge in urological practice.The lifetime prevalence of urolithiasis ranges from approximately 5%–15%worldwide has clearly increased trend over recent decades1–3.Moreover,up to half of patients experience recurrent episodes within 5–10 years,4,5resulting in repeated interventions and cumulative morbidity.As a consequence,a substantial proportion of patients present with complex renal stone disease characterized by a large stone burden,infection,hydronephrosis,or impaired renal function.6展开更多
Dear Editor,We present a case of acute zonal occult outer retinopathy(AZOOR)complex in a myopic patient with angioid streaks(ASs).A 19-year-old female has been experiencing visual field defects in her left eye for mor...Dear Editor,We present a case of acute zonal occult outer retinopathy(AZOOR)complex in a myopic patient with angioid streaks(ASs).A 19-year-old female has been experiencing visual field defects in her left eye for more than 3y.She was diagnosed with ASs and choroiditis at a local hospital.She has a seven-year history of bilateral high myopia.A fundus examination confirmed the presence of ASs and myopic fundus changes in both eyes.Multimodal imaging revealed an AZOOR complex in the left eye.展开更多
Let F be an additive subfunctor of Ext1.We introduce the concept of F-silting complexes,which is a generalization of F-tilting modules in relative derived categories.Some equivalent characterizations of F-silting c...Let F be an additive subfunctor of Ext1.We introduce the concept of F-silting complexes,which is a generalization of F-tilting modules in relative derived categories.Some equivalent characterizations of F-silting complexes are obtained.Finally,we investigate the relative version of the Bongartz's Theorem and construct a Bongartz's completion for an F-presilting complex.展开更多
Increased crop diversity can alter soil nitrogen(N)levels,soil properties,and functional microbial communities,leading to changes in potential nitrous oxide(N2O)emissions.However,our understanding on relationships ...Increased crop diversity can alter soil nitrogen(N)levels,soil properties,and functional microbial communities,leading to changes in potential nitrous oxide(N2O)emissions.However,our understanding on relationships between N2O emissions and related microbes in diversified rotation systems is still limited.Here,we established a long-term field experiment to investigate the response of N2O emissions regulated by five N-cycling genes in three rotation systems.Our results showed that N2O emissions in wheat and maize seasons in diversified rotations(spring maize→winter wheat–summer maize and spring peanut→winter wheat–summer maize)were 15.5%-51.1%and 15.9%-53.3%lower than that in winter wheat–summer maize rotation(P<0.05),respectively.Diversified rotations decreased abundance of ammonia-oxidizing archaea(AOA)amoA,AOB amoA,nirK and nirS genes in both wheat and maize seasons,while increased abundance of nosZ gene in maize season,leading to lower soil N2O emissions.Changes in these functional genes correlated significantly with soil moisture,nitrogen availability,and enzyme activity(L-leucine aminopeptidase and Urease).Besides,diversified rotations increased number of nodes,edges and degree of the co-occurring network and sub-network,while reduced average path length and betweeness.These microbial co-occurrence network complexity indicators were significantly correlated with N2O emissions.This indicates that increase in aboveground crop diversity drives the increase in complexity of belowground N-cycling related microbial interaction networks,which leads to lower N2O emissions.In summary,diversified rotations show promising potentials to lower N2O emissions in agricultural soils.展开更多
Physics-informed neural networks(PINNs)have emerged as powerful tools for data-driven solutions of partial differential equations.However,when solving complex solutions with a sharp gradient or waveform mutation regio...Physics-informed neural networks(PINNs)have emerged as powerful tools for data-driven solutions of partial differential equations.However,when solving complex solutions with a sharp gradient or waveform mutation region,the traditional PINNs method frequently has significantly higher prediction errors in critical regions than in other areas because of randomly or uniformly distributed sampling points.To overcome the limitations of PINNs in solving complex solutions,we propose a high-residual region resampling PINN(HRR-PINN)method.The HRR-PINN method uses a two-stage paradigm.Pre-training focuses on global modeling to obtain the residual of the network training,which is helpful for achieving a more precise sampling optimization.Secondary training focuses on computational resources of critical regions to specialize in optimizing high-residual regions based on the global results of pretraining,that is,adding new points in high-residual regions and removing low-residual points from the original set.To illustrate the effectiveness of the HRR-PINN method,we applied it to single-periodic solutions,rogue wave solutions on single-periodic backgrounds,and double-periodic solutions of the second-type derivative nonlinear Schr¨odinger equation.Numerical experiments show that the HRR-PINN method significantly optimizes the distribution of sampling points and reduces prediction errors.This confirms the effectiveness for solving complex solutions with abrupt waveform changes or sharp gradients of the HRR-PINN method.展开更多
The mobility and fate of antimony(Sb)in soil and aquatic environments are primarily gocerned its adsorption onto iron oxides(hydroxides),a process markedly influenced by natural organic matter(NOM).In this study,batch...The mobility and fate of antimony(Sb)in soil and aquatic environments are primarily gocerned its adsorption onto iron oxides(hydroxides),a process markedly influenced by natural organic matter(NOM).In this study,batch experiments(kinetic studies,isotherm analyses,and pH effect evaluations)were conducted to examine Sb(V)adsorption onto Hematite-Humic complexes(Hem-HA complexes)as representative organic-inorganic hybrid materials.HA treatment did not modify the crystal structure of Hem.However,the resulting Hem-HA complexes exhibited reduced surface area,porosity,and pore diameter compared to unmodified Hem.The adsorption of Sb(V)was significantly affected by HA concentration and pH.The maximum adsorption capacity of Hem-HA complexes was lower than that of Hem and gradually decreased as the HA treatment concentration increased.The incorporation of HA onto Hem surfaces reduced the number of reactive adsorption sites,increasing the mobility risk of Sb(V).Sb(V)adsorption was favored under acidic conditions,with Hem-HA4showing a decrease in maximum adsorption capacity from 4.24 to 2.05 mg/g as pH rose from 3 to 9.The adsorption process followed pseudo-second-order kinetics and was well described by both the Langmuir and Freundlich models,indicating a monolayer adsorption mechanism.Spectroscopic analyses(Fourier transform infrared and X-ray absorption spectroscopy)confirmed the formation of Fe-O-Sb monodentate,mononuclear edge-sharing inner-sphere complexes via electron sharing or transfer.Direct complexation between organic functional groups and Sb(V)was also observed.These findings enhance our understanding of Sb biogeochemical cycling and offer valuable insights for Sb remediation in complex environmental systems.展开更多
The photochemical transformation of fluoroquinolones(FQs) represents a crucial environmental phenomenon eliciting growing concern. Nevertheless, the impact and mechanisms of ubiquitously coexisting copper ions, i.e.,...The photochemical transformation of fluoroquinolones(FQs) represents a crucial environmental phenomenon eliciting growing concern. Nevertheless, the impact and mechanisms of ubiquitously coexisting copper ions, i.e.,Cu(Ⅱ), remain elusive. Here, the role of Cu(Ⅱ) in the photochemical transformation of FQs was systematically investigated via experimental characterizations and theoretical simulations. Cu(Ⅱ) markedly inhibited the photolysis of levofloxacin(LEV), a representative FQs model, from 0.0078 to 0.0040 min-1 after a 100-min irradiation under simulated sunlight with the molar ratio of Cu(Ⅱ): LEV at 1:1. The micro-level mechanisms were explored, including the ligand-to-metal charge transfer in complexation, modifications to reactive sites and activities with various reactive species, and higher hole-electron separation extents. In addition, the triplet excited state, singlet oxygen, and hydroxyl radical in LEV and LEV-Cu(Ⅱ) with 1:1 molar ratio played pivotal roles in the transformation, contributing 20.77 %/20.02 %, 13.87 %/14.59 %, and 7.96 %/4.68 %, respectively. Furthermore, considering more FQs models, the inhibition of Cu(Ⅱ) on the transformation was found to universally exist in ciprofloxacin, enoxacin, enrofloxacin, norfloxacin, ofloxacin and pefloxacin, and their multiple molecular descriptors were changed with a same tendency. This work provides a comprehensive understanding of the transformation of antibiotics within complex aqueous matrices, contributing to further estimation of antibiotics removal and ecological risks.展开更多
Cisplatin(CDDP)-based chemotherapy is an effective strategy for the treatment of advanced nasopharyngeal carcinoma(NPC).However,serious toxic side effects of CDDP limit patient tolerance and treatment compliance,which...Cisplatin(CDDP)-based chemotherapy is an effective strategy for the treatment of advanced nasopharyngeal carcinoma(NPC).However,serious toxic side effects of CDDP limit patient tolerance and treatment compliance,which urgently needs to be addressed in clinical application.Liposomes have been considered ideal vehicles for reducing CDDP toxicity due to their high biocompatibility,low toxicity and passive targeting ability.Nevertheless,CDDP's poor water/lipid solubility usually results in a low liposome druglipid ratio,limiting tumor delivery ability.Herein,a CDDP-polyphenol complex liposome was designed to increase the drug loading capacity of CDDP to realize the reduction of toxicity and effective antitumor effect simultaneously.The complex was prepared via complexation reaction of different stoichiometric ratios of CDDP and polyphenolic substances(gallic acid,epigallocatechin gallate and tannic acid),followed by encapsulation of complex in liposomes to improve tumor targeting.Notably,the molecular interaction forces between CDDP and polyphenolic substances were intensively investigated through a binding force disruption assay.In vitro studies demonstrated that the optimal formulation of CDDP-epigallocatechin gallate complex liposome(CDDP-EGCG Lips) showed the highest CDDP encapsulation efficiency,favorable stability,pH-sensitive release,enhanced cellular uptake and apoptosis effect.In vivo studies revealed that CDDP-EGCG Lips retarded the elimination of CDDP to prolong their circulation time,inhibited the growth of tumors,and significantly reduced the toxic side effects compared to CDDP monotherapy.This delivery strategy holds great promise for improving the clinical use of platinum-based drugs.展开更多
Herein,this work used n-butylamine addition and NH3atmosphere activation to optimize a vanadium phosphorus oxide catalyst.By comparing the low-temperature NH3-SCR activity,complex nitrogen modified samples(VPO-2...Herein,this work used n-butylamine addition and NH3atmosphere activation to optimize a vanadium phosphorus oxide catalyst.By comparing the low-temperature NH3-SCR activity,complex nitrogen modified samples(VPO-2B-NH3)performed best(>90%at 200–270°C).XRD,Raman,and HRTEM results revealed a transition from the VOPO 4 phase to the amorphous phase after the n-butylamine addition.Complex nitrogen modification increased the specific surface area,surface acidity,enrichment of surface oxygen vacancies,and the ratios of V4+/(V4++V5+)and Oads/(Oads+Olatt).In addition,the in-situ DRIFTs results indicated that the prepared catalyst simultaneously followed the Eley-Rideal(E-R)and Langmuir-Hinshelwood(L-H)mechanisms.Complex nitrogen modification was used to improve NH3-SCR performance by accelerating consumption of surface NH3(on Lewis acid sites)and NO 2 species and decreasing the deposition of these species after the sustained reaction.This rationally elucidates the effect of complex nitrogen modification on the stability of the vanadium phosphorus oxide catalyst.展开更多
Unmanned aerial vehicles(UAVs)are widely utilized in area coverage tasks due to their flexibility and efficiency in geo-graphic information acquisition.However,complex boundary conditions in actual water area maps oft...Unmanned aerial vehicles(UAVs)are widely utilized in area coverage tasks due to their flexibility and efficiency in geo-graphic information acquisition.However,complex boundary conditions in actual water area maps often reduce coverage efficiency.To address this issue,this paper proposes a map preprocessing algorithm that linearizes boundary lines and processes concave areas into concave polygons,followed by gridding the map.Additionally,a collaborative area coverage method for UAV swarms is introduced based on region partitioning,which considers the comprehensive cost of energy consumption and time.An improved Hungarian algorithm is utilized for region partitioning,and a Dubins-A*-based plow-ing area full coverage path planning method is proposed to achieve path smoothing and collaborative coverage of each partition.Two sets of simulation experiments are conducted.The first experiment verifies the effectiveness of the map preprocessing algorithm,and the second compares the proposed collaborative area coverage algorithm with other methods,demonstrating its performance advantages.展开更多
Air pollution in China exhibits complex characteristics,involving the coupling of multiple pollutants across various media and processes.This has led to PM2.5and O3concentrations far exceeding the World Health O...Air pollution in China exhibits complex characteristics,involving the coupling of multiple pollutants across various media and processes.This has led to PM2.5and O3concentrations far exceeding the World Health Organization(WHO)guideline values,posing significant risks to public health and safety.While this severe pollution presents a major environmental challenge,it also offers critical opportunities for advancing atmospheric science research.This review summarizes the research progress made by the Research Center for Eco-Environmental Sciences,Chinese Academy of Sciences(RCEES-CAS)over the past decade in elucidating the causes of air pollution complex and developing control technologies for key pollutants.Significant breakthroughs in understanding air pollution mechanisms include:(1)elucidating the activation mechanism of O2and the synergistic effects of multi pollutant gases transformations at interfaces;(2)revealing the critical role of aerosol surface reactions in enhancing atmospheric oxidation capacity and driving the explosive growth of secondary particulate matter.Building on these findings,He's team together with domestic peers proposed the concept and research framework of"atmospheric haze chemistry".Distinct from the cloud chemistry of London smog and the photochemical processes of Los Angeles smog,this framework provides an updated theoretical foundation for understanding the unique mechanisms underlying China's air pollution complex.In pollution control technology,RCEES-CAS has developed advanced solutions for key pollutants such as NOx,VOCs,NH3,and O3,employing methods including adsorption,catalytic decomposition,selective catalytic reduction(SCR),and catalytic oxidation.Several well-established technologies have been successfully implemented,making significant contributions to air pollution mitigation in China.Additionally,an integrated carbon-neutral fuel strategy has been explored,combining green hydrogen production,biomass valorization,and CO2conversion.Finally,this review discusses the challenges and future prospects in advancing atmospheric haze chemistry theory and achieving sustained improvements in air quality.展开更多
The Guidong complex in northern Guangdong constitutes a key segment of the Nanling Metallogenic Belt and hosts significant granite-related uranium deposits.However,the petrogenesis of the Yanshanian intrusions in its ...The Guidong complex in northern Guangdong constitutes a key segment of the Nanling Metallogenic Belt and hosts significant granite-related uranium deposits.However,the petrogenesis of the Yanshanian intrusions in its western part remains poorly constrained because of insufficient high-precision geochronological and mineralogical data.This limitation hinders a comprehensive understanding of regional metallogenesis.To address this,we conducted an integrated study of the Siqian two-mica granite and the Changping biotite granite,incorporating zircon U-Pb geochronology,whole-rock geochemistry,Hf-Nd isotope analysis,and mineral chemistry.Our objectives were to determine their emplacement ages and to investigate their petrogenesis and relationship with uranium mineralization.Zircon U-Pb dating indicates that the Siqian and Changping granites formed at 160±1 Ma and 156±1 Ma,respectively,suggesting both were emplaced during the Early Yanshanian magmatic event.These high-K calc-alkaline rocks are peraluminous(A/CNK=1.04-1.44),enriched in large-ion lithophile elements(LILEs;e.g.,Rb,Th,U),and depleted in high-field-strength elements(HFSEs;e.g.,Ba,Nb,Ta).They exhibit negative zircon εHf(t)values ranging from-15.4 to-8.4,with corresponding crustal model ages of 1668-2142 Ma.Whole-rock samples show εNd(t)values from-11.2 to-9.1 and Nd model ages of 1693-1860 Ma.These isotopic features indicate that both plutons represent moderately differentiated S-type granites derived from partial melting of Paleo-to Mesoproterozoic metasedimentary sources(e.g.,pelitic and psammitic rocks),accompanied by fractional crystallization of minerals such as ilmenite and apatite.Integrated geochemical and mineralogical data reveal that the Siqian and Changping granites are characterized by low Th/U ratios,high F contents,and low magmatic oxygen fugacity—signatures typical of U-rich granites.These attributes provided a favorable lithogeochemical environment for uranium enrichment and acted as primary sources for uranium-bearing,high-temperature hydrothermal fluids,thereby playing a critical role in regional uranium mineralization.展开更多
An integrated dynamic model updating method is proposed to address the challenges of mode jumping and mode degeneracy for complex dynamic models.A reduced order proxy model of Neural Network Response Surface(NNRS)was ...An integrated dynamic model updating method is proposed to address the challenges of mode jumping and mode degeneracy for complex dynamic models.A reduced order proxy model of Neural Network Response Surface(NNRS)was constructed by Modal Matching Reconstruction Strategy(MMRS)and an Improved Vectorial Surrogate Model(IVSM).Among them,the analytical modes are correctly matched with the experimental modes by MMRS,and the order of the mode matching is determined by calculating the Modal Assurance Criterion(MAC),addressing the dynamic changes of the mode matching order during the construction of the NNRS.The fitted NNRS model results are vectorized by IVSM,enabling the rapid extraction of required input and output parameters under multi-parameter conditions,thereby improving efficiency.The model parameters are updated using a multi-objective genetic algorithm,which achieves the simultaneous updating of natural frequency and mode shape.To validate the accuracy and efficiency,an intermediate casing of a gas turbine was updated using the proposed method.With high efficiency,the mean absolute error of natural frequency for the matched order decreased from 24.46%to 3.89%,while the corresponding average MAC value increased from 0.654 to 0.752.展开更多
The Mechanism for Air pollution compleX version 1.0(MAX1),describing detailed tropospheric chemical processes,has been developed based on the latest knowledge.MAX1 contains 940 reactions,including photolysis,gaseous r...The Mechanism for Air pollution compleX version 1.0(MAX1),describing detailed tropospheric chemical processes,has been developed based on the latest knowledge.MAX1 contains 940 reactions,including photolysis,gaseous reactions,and heterogeneous reactions of 300 species,which is adequate for both box model and climate transport model(CTM)applications.Detailed chemical processes of chlorine chemistry,chemistry of Criegee intermediates,and heterogeneous uptake of HO2 and N2O5 have been implemented and updated.With this level of explicitness,MAX1 can support investigations into the quantification of secondary pollutant productions and the chemical behavior of the crucial intermediates,such as organic peroxy radicals.Box model and CTM tests were conducted to evaluate the performance of MAX1 from different perspectives.Simulations of MAX1 successfully captured the variation of ozone in all cases tested.Meanwhile,significant improvement was made on predictions of radicals compared to other mechanisms,especially under the low NOx environment,with good similarity to simulations of a nearly explicit chemical mechanism(i.e.,Master Chemical Mechanism)that contains over 17000 reactions.The computational expense of MAX1 is acceptable and it can be applied in atmospheric scientific research and air quality prediction.MAX1 introduces new dimensions in atmospheric chemistry modeling,and its potential application in policymaking is a promising yet exploratory step.It offers improved insights into air quality dynamics,which could assist policymakers in making more informed decisions.However,the translation of its detailed chemical understanding into practical strategies remains an area for further investigation.This model suggests a path towards more nuanced air pollution control methods,contributing to ongoing efforts in environmental management.展开更多
Over the past five decades,the Research Center for Eco-Environmental Sciences of the Chinese Academy of Sciences(CAS)and its predecessor and associated laboratories—including the Key Laboratory of Systems Ecology of ...Over the past five decades,the Research Center for Eco-Environmental Sciences of the Chinese Academy of Sciences(CAS)and its predecessor and associated laboratories—including the Key Laboratory of Systems Ecology of CAS(established in 1986),the State Key Laboratory of Urban and Regional Ecology(established in 2006),and the recently approved State Key Laboratory of Regional and Urban Ecology(2025)—have made seminal contributions to the development and application of the social-economic-natural complex ecosystem(SENCE)theory.Initially proposed in 1984 by Shijun Ma and Rusong Wang,SENCE theory is an interdisciplinary,holistic,and integrative framework for understanding the complex interactions and feedback mechanisms between social,economic,and natural subsystems.SENCE theory has underpinned the development of the pattern–process–service–sustainability(PPSS)research paradigm,which has been used to systematically analyze the dynamics of fragile ecosystems such as the Loess Plateau and to design innovative solutions for ecological restoration and sustainable regional development.The theory has also significantly advanced research in ecosystem services and ecological security,providing the scientific basis for key national initiatives such as ecological function zoning,the ecological conservation redline policy,and the establishment of China's national park system.Furthermore,the development and application of SENCE theory have catalyzed the emergence of urban ecology as a distinct interdisciplinary field in China,exemplified by the establishment of the country's first urban ecosystem research station in Beijing.This station has generated long-term ecological data on,novel theoretical insights into,and practical policy support for sustainable urban planning and management.In addition,grounded in SENCE theory,a series of pioneering sustainability models have been developed and implemented,including China's first“ecological province”(Hainan),“ecological city”(Yangzhou),“ecological county”(Dafeng),and the first national pilot program for realizing the value of ecological products(Lishui).These models have shown how the SENCE approach can effectively bridge ecological conservation and socio-economic development,providing practical pathways for regional sustainability.Looking ahead,SENCE research will continue to advance theoretical understanding,enhance computational modeling and simulation capabilities,and strengthen evidence-based policy-making.By aligning with China's national ecological civilization strategy as well as global sustainability agendas,future research within this framework will not only inform the construction of a“Beautiful China”but also contribute Chinese wisdom and solutions to global ecological governance.展开更多
The conversion of molecular dinitrogen(N2)into ammonia(NH3)is one of the most important chemical pro-cesses.The hemilabile axial bonding in the transition metal(TM)complexes with d-p,d-d and d-df interactions could pr...The conversion of molecular dinitrogen(N2)into ammonia(NH3)is one of the most important chemical pro-cesses.The hemilabile axial bonding in the transition metal(TM)complexes with d-p,d-d and d-df interactions could provide an electron reservoir that controls the evolution of the oxidation state on the active center,which is potential to facilitate N2-to-NH3 conversion.In this perspective,the bionic nitrogen fixing process is illustrated on a molecular level,which features flexible axial bonding to regulate"electron reservoir".The comprehensive overview summarizes the features of TM complexes with axial supporting ligand and focuses on how the axial"assistant"atom tunes the electronic properties of the metal center to facilitate dinitrogen binding,as well as proton/electron delivery in N2 reduction.To illustrate the mechanism of axial"electron reservoir"in dinitrogen fixation on different TM complexes with axial supporting ligand,the relationships of geometric parameters,the variation of electronic structure and oxidation state,the influence principles of axial bonding regulated by an-chor atoms,the critical roles of peripheral ligands and the overall comprehension from orbital interaction are all involved.A preliminary view of the major challenges and future opportunities of TM dinitrogen complexes with flexible axial bonding is highlighted at the end.Through this perspective,we hope to give a comprehensive demonstration of the flexible axial bonding as"electron reservoir"in dinitrogen fixation,and shed light on the rational design for fabricating efficient catalysts in the future.展开更多
To investigate the antitumor properties of copper(Ⅱ)complexes,a series of Cucomplexes(C1-C3)derived from 6,7-dihydro-5H-quinoline-8-one thiosemicarbazone ligands was designed and synthesized.These complexes exhibited...To investigate the antitumor properties of copper(Ⅱ)complexes,a series of Cucomplexes(C1-C3)derived from 6,7-dihydro-5H-quinoline-8-one thiosemicarbazone ligands was designed and synthesized.These complexes exhibited significantly higher potency in inhibiting tumor cell growth in vitro compared to cisplatin.Among them,C3 had the highest antitumor activity against MDA-MB-231 cells,with a half maximal inhibitory concentration(IC50)value of 1.42μmol·L-1.Moreover,C3 effectively inhibited the growth of 3D multicellular spheres.Mechanistically,it induced significant reactive oxygen species(ROS)generation,initiating a dual-pathway cytotoxic effect.On the one hand,it triggers endoplasmic reticulum stress and inhibits the activity of the related protein,protein disulfide isomerase(PDI).On the other hand,it induces mitochondrial dysfunction.These combined stresses ultimately lead to the apoptosis of MDA-MB-231 cells.展开更多
To develop highly stable and active Ru complex catalysts for CO2hydrogenation,we synthesized Ru complexes bearing rigid pincer-type tridentate NNN(pyrazole-pyridine-pyrazole)ligands and weakly coordinated triphenyl...To develop highly stable and active Ru complex catalysts for CO2hydrogenation,we synthesized Ru complexes bearing rigid pincer-type tridentate NNN(pyrazole-pyridine-pyrazole)ligands and weakly coordinated triphenylphosphine(PPh3)ligands.The NNN ligands can strongly chelate with the Ru metal center,contributing to the overall robustness of the catalytic system.Meanwhile,PPh3 can easily dissociate to form vacant coordination sites,thereby enhancing catalytic activity.As a result,the Ru-NNN complex[Ru(L-NNN)Cl(PPh3)2]Cl(1,L-NNN=2,6bis(5-methyl-1H-pyrazol-3-yl)pyridine)was not only quite stable,but also showed high activity for CO2hydrogenation to formate,achieving a TON of up to 150000.In the mechanism study,based on the results of in-situ NMR,in-situ HPLC-HRMS spectra,and density functional theory calculations,it is speculated that the active intermediates with empty coordination sites are highly active species in CO2hydrogenation.展开更多
Symmetry-breaking structural phase transitions in spin crossover(SCO)complexes play a pivotal role in the development of multifunctional SCO materials.In this work,the influence of counter anions on the symmetry-break...Symmetry-breaking structural phase transitions in spin crossover(SCO)complexes play a pivotal role in the development of multifunctional SCO materials.In this work,the influence of counter anions on the symmetry-breaking behavior and SCO properties was investigated in three mononuclear FeⅢ-qsal type complexes,[Fe(qsal-4-Me)2]A(Hqsal-4-Me=4-methyl-N-(8-quinolyl)salicylaldimine;A=BF4-(1_(BF4)),ClO4-(2_(ClO4)),and OTf-(3OTf)).All complexes exhibit a typical"Chain-Layer"structural motif.Single-crystal structural analysis at varying temperatures(50-400 K for 1_(BF4) and 120-300 K for 2_(ClO4))revealed distinct symmetry-breaking behaviors in 1_(BF4) and 2_(ClO4).Notably,1_(BF4) undergoes complete symmetry-breaking and re-entrant behavior,coupled with a three-step SCO,while 2_(ClO4) shows only symmetry-breaking incomplete SCO without re-entrance.Structure analyses indicated that the more compact crystal packing in 2_(ClO4)strengthens the elastic interactions between the high-spin FeⅢcenters.This stabilizes the low-spin/high-spin[LS-HS]intermediate phase,thereby inhibiting the reentrant behavior.Compound 3OTf with the largest OTf-anion remains in the HS state below 400 K.While 1_(BF4) showed no LIESST effect,2_(ClO4) displayed a rare reverse-LIESST effect upon irradiation with 980 nm light.The findings reported here demonstrate that subtle variations in anion type can dramatically modulate SCO behavior,offering valuable insights for the design of functional materials with tailored spin transitions.展开更多
基金Supported by the Natural Science Foundation of Shandong Province(No.ZR2018LD009)。
摘要Three photosystem I(PSⅠ)particles associated with different amounts of light-harvesting complex I(LHCI)were isolated from a phycocyanin 645(PC645)-containing cryptophyte Chroomonas placoidea by Triton X-100 sucrose gradient centrifugation.Two active PSⅠ-LHCⅠparticles(Bands 4 and 5)were resolved from thylakoids stripped of cations only,which implied that LHC migration and the adjustment of energy distribution between photosystemⅡ(PSⅡ)and PSⅠfacilitated by cations could also occur in cryptophytes,like in higher plants.Peptide analysis revealed that 19.8-,10-,and 8.3-kDa peptides corresponding toβ,α1,andα2 subunits of PC645,respectively,were present in Bands 4 and 5.Analyses of fluorescence and circular dichroism spectra and Gauss analyses revealed efficient energy couplings between PC645 and chlorophyll within both of these PSⅠ-LHCⅠparticles.The excitation energy absorbed by PC645 could be directly transferred to chlorophyll a in the PSⅠcore or via the chlorophyll a/c-protein complex of LHCⅠ.Based on these observations,we designated the two PSⅠ-LHCⅠparticles as phycocyanin-PSⅠcomplexes,which have not been reported previously.Band 4-2 was a sub-complex of Band 4 and was almost depleted of LHCⅠ(the chlorophyll a/c-protein complex was designated as Band 4-1)and PC645.Therefore,Band 4-2 was recognized as the PSⅠcore complex.Negative staining and transmission electron microscopy images of Band 4 gave a direct view that the PC645 component attached with chlorophyll-protein complexes in a regular structure as hollow ring shape.Furthermore,while previous studies have indicated that PC645 associates with PSⅡ,our results reveal that,in this cryptophytic alga,PC645 exhibits structural—but not preferential—association with PSⅠ,which provided new information about the architecture and function of the energy transfer system comprising phycobiliproteins and chlorophyll-protein complexes in cryptophytes.
基金supported by the Natural Science Foundation of Zhejiang Province,China(No.LTGD23H050001 to Jie Yuan).
摘要Complex renal calculi,including staghorn and multiple renal stones,remain a significantchallenge in urological practice.The lifetime prevalence of urolithiasis ranges from approximately 5%–15%worldwide has clearly increased trend over recent decades1–3.Moreover,up to half of patients experience recurrent episodes within 5–10 years,4,5resulting in repeated interventions and cumulative morbidity.As a consequence,a substantial proportion of patients present with complex renal stone disease characterized by a large stone burden,infection,hydronephrosis,or impaired renal function.6
基金Supported by the National Natural Science Foundation of China(No.82171073).
摘要Dear Editor,We present a case of acute zonal occult outer retinopathy(AZOOR)complex in a myopic patient with angioid streaks(ASs).A 19-year-old female has been experiencing visual field defects in her left eye for more than 3y.She was diagnosed with ASs and choroiditis at a local hospital.She has a seven-year history of bilateral high myopia.A fundus examination confirmed the presence of ASs and myopic fundus changes in both eyes.Multimodal imaging revealed an AZOOR complex in the left eye.
基金Supported by NSFC(No.12071120)Basic Research Program(Free Exploration)Youth Scientific Research Project of Shanxi Province(No.202403021212001)。
摘要Let F be an additive subfunctor of Ext1.We introduce the concept of F-silting complexes,which is a generalization of F-tilting modules in relative derived categories.Some equivalent characterizations of F-silting complexes are obtained.Finally,we investigate the relative version of the Bongartz's Theorem and construct a Bongartz's completion for an F-presilting complex.
基金supported by the National Key Research and Development Program of China(No.2022YFD2300803)the National Natural Science Foundation of China(Nos.32172125 and 31901470).
摘要Increased crop diversity can alter soil nitrogen(N)levels,soil properties,and functional microbial communities,leading to changes in potential nitrous oxide(N2O)emissions.However,our understanding on relationships between N2O emissions and related microbes in diversified rotation systems is still limited.Here,we established a long-term field experiment to investigate the response of N2O emissions regulated by five N-cycling genes in three rotation systems.Our results showed that N2O emissions in wheat and maize seasons in diversified rotations(spring maize→winter wheat–summer maize and spring peanut→winter wheat–summer maize)were 15.5%-51.1%and 15.9%-53.3%lower than that in winter wheat–summer maize rotation(P<0.05),respectively.Diversified rotations decreased abundance of ammonia-oxidizing archaea(AOA)amoA,AOB amoA,nirK and nirS genes in both wheat and maize seasons,while increased abundance of nosZ gene in maize season,leading to lower soil N2O emissions.Changes in these functional genes correlated significantly with soil moisture,nitrogen availability,and enzyme activity(L-leucine aminopeptidase and Urease).Besides,diversified rotations increased number of nodes,edges and degree of the co-occurring network and sub-network,while reduced average path length and betweeness.These microbial co-occurrence network complexity indicators were significantly correlated with N2O emissions.This indicates that increase in aboveground crop diversity drives the increase in complexity of belowground N-cycling related microbial interaction networks,which leads to lower N2O emissions.In summary,diversified rotations show promising potentials to lower N2O emissions in agricultural soils.
基金supported by the National Natural Science Foundation of China(Grant Nos.12547136,12575002,and 12235007).
摘要Physics-informed neural networks(PINNs)have emerged as powerful tools for data-driven solutions of partial differential equations.However,when solving complex solutions with a sharp gradient or waveform mutation region,the traditional PINNs method frequently has significantly higher prediction errors in critical regions than in other areas because of randomly or uniformly distributed sampling points.To overcome the limitations of PINNs in solving complex solutions,we propose a high-residual region resampling PINN(HRR-PINN)method.The HRR-PINN method uses a two-stage paradigm.Pre-training focuses on global modeling to obtain the residual of the network training,which is helpful for achieving a more precise sampling optimization.Secondary training focuses on computational resources of critical regions to specialize in optimizing high-residual regions based on the global results of pretraining,that is,adding new points in high-residual regions and removing low-residual points from the original set.To illustrate the effectiveness of the HRR-PINN method,we applied it to single-periodic solutions,rogue wave solutions on single-periodic backgrounds,and double-periodic solutions of the second-type derivative nonlinear Schr¨odinger equation.Numerical experiments show that the HRR-PINN method significantly optimizes the distribution of sampling points and reduces prediction errors.This confirms the effectiveness for solving complex solutions with abrupt waveform changes or sharp gradients of the HRR-PINN method.
基金supported by the National Natural Science Foundation of China(Nos.42030706 and 42077182).
摘要The mobility and fate of antimony(Sb)in soil and aquatic environments are primarily gocerned its adsorption onto iron oxides(hydroxides),a process markedly influenced by natural organic matter(NOM).In this study,batch experiments(kinetic studies,isotherm analyses,and pH effect evaluations)were conducted to examine Sb(V)adsorption onto Hematite-Humic complexes(Hem-HA complexes)as representative organic-inorganic hybrid materials.HA treatment did not modify the crystal structure of Hem.However,the resulting Hem-HA complexes exhibited reduced surface area,porosity,and pore diameter compared to unmodified Hem.The adsorption of Sb(V)was significantly affected by HA concentration and pH.The maximum adsorption capacity of Hem-HA complexes was lower than that of Hem and gradually decreased as the HA treatment concentration increased.The incorporation of HA onto Hem surfaces reduced the number of reactive adsorption sites,increasing the mobility risk of Sb(V).Sb(V)adsorption was favored under acidic conditions,with Hem-HA4showing a decrease in maximum adsorption capacity from 4.24 to 2.05 mg/g as pH rose from 3 to 9.The adsorption process followed pseudo-second-order kinetics and was well described by both the Langmuir and Freundlich models,indicating a monolayer adsorption mechanism.Spectroscopic analyses(Fourier transform infrared and X-ray absorption spectroscopy)confirmed the formation of Fe-O-Sb monodentate,mononuclear edge-sharing inner-sphere complexes via electron sharing or transfer.Direct complexation between organic functional groups and Sb(V)was also observed.These findings enhance our understanding of Sb biogeochemical cycling and offer valuable insights for Sb remediation in complex environmental systems.
基金supported by the National Natural Science Foundation of China(No.22378232)the Young Scholars Program of Shandong University,Taishan Scholars Project of Shandong Province(No.tstp20230604)Qingdao Postdoctoral Project Funding(No.QDBSH20230202021).
摘要The photochemical transformation of fluoroquinolones(FQs) represents a crucial environmental phenomenon eliciting growing concern. Nevertheless, the impact and mechanisms of ubiquitously coexisting copper ions, i.e.,Cu(Ⅱ), remain elusive. Here, the role of Cu(Ⅱ) in the photochemical transformation of FQs was systematically investigated via experimental characterizations and theoretical simulations. Cu(Ⅱ) markedly inhibited the photolysis of levofloxacin(LEV), a representative FQs model, from 0.0078 to 0.0040 min-1 after a 100-min irradiation under simulated sunlight with the molar ratio of Cu(Ⅱ): LEV at 1:1. The micro-level mechanisms were explored, including the ligand-to-metal charge transfer in complexation, modifications to reactive sites and activities with various reactive species, and higher hole-electron separation extents. In addition, the triplet excited state, singlet oxygen, and hydroxyl radical in LEV and LEV-Cu(Ⅱ) with 1:1 molar ratio played pivotal roles in the transformation, contributing 20.77 %/20.02 %, 13.87 %/14.59 %, and 7.96 %/4.68 %, respectively. Furthermore, considering more FQs models, the inhibition of Cu(Ⅱ) on the transformation was found to universally exist in ciprofloxacin, enoxacin, enrofloxacin, norfloxacin, ofloxacin and pefloxacin, and their multiple molecular descriptors were changed with a same tendency. This work provides a comprehensive understanding of the transformation of antibiotics within complex aqueous matrices, contributing to further estimation of antibiotics removal and ecological risks.
基金supported by the National Natural Science Foundation of China (Nos.81872823,82073782,and 82241002)the Key R&D Plan of Ganjiang New District of Jiangxi (No.2023010)。
摘要Cisplatin(CDDP)-based chemotherapy is an effective strategy for the treatment of advanced nasopharyngeal carcinoma(NPC).However,serious toxic side effects of CDDP limit patient tolerance and treatment compliance,which urgently needs to be addressed in clinical application.Liposomes have been considered ideal vehicles for reducing CDDP toxicity due to their high biocompatibility,low toxicity and passive targeting ability.Nevertheless,CDDP's poor water/lipid solubility usually results in a low liposome druglipid ratio,limiting tumor delivery ability.Herein,a CDDP-polyphenol complex liposome was designed to increase the drug loading capacity of CDDP to realize the reduction of toxicity and effective antitumor effect simultaneously.The complex was prepared via complexation reaction of different stoichiometric ratios of CDDP and polyphenolic substances(gallic acid,epigallocatechin gallate and tannic acid),followed by encapsulation of complex in liposomes to improve tumor targeting.Notably,the molecular interaction forces between CDDP and polyphenolic substances were intensively investigated through a binding force disruption assay.In vitro studies demonstrated that the optimal formulation of CDDP-epigallocatechin gallate complex liposome(CDDP-EGCG Lips) showed the highest CDDP encapsulation efficiency,favorable stability,pH-sensitive release,enhanced cellular uptake and apoptosis effect.In vivo studies revealed that CDDP-EGCG Lips retarded the elimination of CDDP to prolong their circulation time,inhibited the growth of tumors,and significantly reduced the toxic side effects compared to CDDP monotherapy.This delivery strategy holds great promise for improving the clinical use of platinum-based drugs.
基金supported by National Natural Science Foundation of China(No.52376088)the University synergy innovation program of Anhui province(No.GXXT-2022–025)the Key Laboratory of Metallurgical Emission Reduction&Resources Recycling by Ministry of Education at Anhui University of Technology(No.JKF23–04).
摘要Herein,this work used n-butylamine addition and NH3atmosphere activation to optimize a vanadium phosphorus oxide catalyst.By comparing the low-temperature NH3-SCR activity,complex nitrogen modified samples(VPO-2B-NH3)performed best(>90%at 200–270°C).XRD,Raman,and HRTEM results revealed a transition from the VOPO 4 phase to the amorphous phase after the n-butylamine addition.Complex nitrogen modification increased the specific surface area,surface acidity,enrichment of surface oxygen vacancies,and the ratios of V4+/(V4++V5+)and Oads/(Oads+Olatt).In addition,the in-situ DRIFTs results indicated that the prepared catalyst simultaneously followed the Eley-Rideal(E-R)and Langmuir-Hinshelwood(L-H)mechanisms.Complex nitrogen modification was used to improve NH3-SCR performance by accelerating consumption of surface NH3(on Lewis acid sites)and NO 2 species and decreasing the deposition of these species after the sustained reaction.This rationally elucidates the effect of complex nitrogen modification on the stability of the vanadium phosphorus oxide catalyst.
基金National Natural Science Foundation of China(62402020,62303022)Beijing Nova Program(20240484720)+1 种基金Project of Cultivation for Young Top-Notch Talents of Beijing Municipal Institutions(BPHR202203043)BTBU Digital Business Platform Project byBMEC.
摘要Unmanned aerial vehicles(UAVs)are widely utilized in area coverage tasks due to their flexibility and efficiency in geo-graphic information acquisition.However,complex boundary conditions in actual water area maps often reduce coverage efficiency.To address this issue,this paper proposes a map preprocessing algorithm that linearizes boundary lines and processes concave areas into concave polygons,followed by gridding the map.Additionally,a collaborative area coverage method for UAV swarms is introduced based on region partitioning,which considers the comprehensive cost of energy consumption and time.An improved Hungarian algorithm is utilized for region partitioning,and a Dubins-A*-based plow-ing area full coverage path planning method is proposed to achieve path smoothing and collaborative coverage of each partition.Two sets of simulation experiments are conducted.The first experiment verifies the effectiveness of the map preprocessing algorithm,and the second compares the proposed collaborative area coverage algorithm with other methods,demonstrating its performance advantages.
基金supported by the National Natural Science Foundation of China(No.22188102)the National Key R&D Program of China(Nos.2022YFC3701004 and 2022YFC3701200)the Youth Innovation Promotion Association,Chinese Academy of Sciences(Nos.Y2022021 and Y2022023)。
摘要Air pollution in China exhibits complex characteristics,involving the coupling of multiple pollutants across various media and processes.This has led to PM2.5and O3concentrations far exceeding the World Health Organization(WHO)guideline values,posing significant risks to public health and safety.While this severe pollution presents a major environmental challenge,it also offers critical opportunities for advancing atmospheric science research.This review summarizes the research progress made by the Research Center for Eco-Environmental Sciences,Chinese Academy of Sciences(RCEES-CAS)over the past decade in elucidating the causes of air pollution complex and developing control technologies for key pollutants.Significant breakthroughs in understanding air pollution mechanisms include:(1)elucidating the activation mechanism of O2and the synergistic effects of multi pollutant gases transformations at interfaces;(2)revealing the critical role of aerosol surface reactions in enhancing atmospheric oxidation capacity and driving the explosive growth of secondary particulate matter.Building on these findings,He's team together with domestic peers proposed the concept and research framework of"atmospheric haze chemistry".Distinct from the cloud chemistry of London smog and the photochemical processes of Los Angeles smog,this framework provides an updated theoretical foundation for understanding the unique mechanisms underlying China's air pollution complex.In pollution control technology,RCEES-CAS has developed advanced solutions for key pollutants such as NOx,VOCs,NH3,and O3,employing methods including adsorption,catalytic decomposition,selective catalytic reduction(SCR),and catalytic oxidation.Several well-established technologies have been successfully implemented,making significant contributions to air pollution mitigation in China.Additionally,an integrated carbon-neutral fuel strategy has been explored,combining green hydrogen production,biomass valorization,and CO2conversion.Finally,this review discusses the challenges and future prospects in advancing atmospheric haze chemistry theory and achieving sustained improvements in air quality.
基金supported by the National Natural Science Foundation of China(grants 42362011 and 42272090)。
摘要The Guidong complex in northern Guangdong constitutes a key segment of the Nanling Metallogenic Belt and hosts significant granite-related uranium deposits.However,the petrogenesis of the Yanshanian intrusions in its western part remains poorly constrained because of insufficient high-precision geochronological and mineralogical data.This limitation hinders a comprehensive understanding of regional metallogenesis.To address this,we conducted an integrated study of the Siqian two-mica granite and the Changping biotite granite,incorporating zircon U-Pb geochronology,whole-rock geochemistry,Hf-Nd isotope analysis,and mineral chemistry.Our objectives were to determine their emplacement ages and to investigate their petrogenesis and relationship with uranium mineralization.Zircon U-Pb dating indicates that the Siqian and Changping granites formed at 160±1 Ma and 156±1 Ma,respectively,suggesting both were emplaced during the Early Yanshanian magmatic event.These high-K calc-alkaline rocks are peraluminous(A/CNK=1.04-1.44),enriched in large-ion lithophile elements(LILEs;e.g.,Rb,Th,U),and depleted in high-field-strength elements(HFSEs;e.g.,Ba,Nb,Ta).They exhibit negative zircon εHf(t)values ranging from-15.4 to-8.4,with corresponding crustal model ages of 1668-2142 Ma.Whole-rock samples show εNd(t)values from-11.2 to-9.1 and Nd model ages of 1693-1860 Ma.These isotopic features indicate that both plutons represent moderately differentiated S-type granites derived from partial melting of Paleo-to Mesoproterozoic metasedimentary sources(e.g.,pelitic and psammitic rocks),accompanied by fractional crystallization of minerals such as ilmenite and apatite.Integrated geochemical and mineralogical data reveal that the Siqian and Changping granites are characterized by low Th/U ratios,high F contents,and low magmatic oxygen fugacity—signatures typical of U-rich granites.These attributes provided a favorable lithogeochemical environment for uranium enrichment and acted as primary sources for uranium-bearing,high-temperature hydrothermal fluids,thereby playing a critical role in regional uranium mineralization.
基金co-supported by the National Major Science and Technology Projects of China(No.2019-I-0019-0018)the Young Scientists Fund of the National Natural Science Foundation of China(No.51905025)。
摘要An integrated dynamic model updating method is proposed to address the challenges of mode jumping and mode degeneracy for complex dynamic models.A reduced order proxy model of Neural Network Response Surface(NNRS)was constructed by Modal Matching Reconstruction Strategy(MMRS)and an Improved Vectorial Surrogate Model(IVSM).Among them,the analytical modes are correctly matched with the experimental modes by MMRS,and the order of the mode matching is determined by calculating the Modal Assurance Criterion(MAC),addressing the dynamic changes of the mode matching order during the construction of the NNRS.The fitted NNRS model results are vectorized by IVSM,enabling the rapid extraction of required input and output parameters under multi-parameter conditions,thereby improving efficiency.The model parameters are updated using a multi-objective genetic algorithm,which achieves the simultaneous updating of natural frequency and mode shape.To validate the accuracy and efficiency,an intermediate casing of a gas turbine was updated using the proposed method.With high efficiency,the mean absolute error of natural frequency for the matched order decreased from 24.46%to 3.89%,while the corresponding average MAC value increased from 0.654 to 0.752.
基金supported by the National Natural Science Foundation of China(Grant Nos.22325601,92044302,42377105)the National Key Scientific and Technological Infrastructure project“Earth System Science Numerical Simulator Facility”.
摘要The Mechanism for Air pollution compleX version 1.0(MAX1),describing detailed tropospheric chemical processes,has been developed based on the latest knowledge.MAX1 contains 940 reactions,including photolysis,gaseous reactions,and heterogeneous reactions of 300 species,which is adequate for both box model and climate transport model(CTM)applications.Detailed chemical processes of chlorine chemistry,chemistry of Criegee intermediates,and heterogeneous uptake of HO2 and N2O5 have been implemented and updated.With this level of explicitness,MAX1 can support investigations into the quantification of secondary pollutant productions and the chemical behavior of the crucial intermediates,such as organic peroxy radicals.Box model and CTM tests were conducted to evaluate the performance of MAX1 from different perspectives.Simulations of MAX1 successfully captured the variation of ozone in all cases tested.Meanwhile,significant improvement was made on predictions of radicals compared to other mechanisms,especially under the low NOx environment,with good similarity to simulations of a nearly explicit chemical mechanism(i.e.,Master Chemical Mechanism)that contains over 17000 reactions.The computational expense of MAX1 is acceptable and it can be applied in atmospheric scientific research and air quality prediction.MAX1 introduces new dimensions in atmospheric chemistry modeling,and its potential application in policymaking is a promising yet exploratory step.It offers improved insights into air quality dynamics,which could assist policymakers in making more informed decisions.However,the translation of its detailed chemical understanding into practical strategies remains an area for further investigation.This model suggests a path towards more nuanced air pollution control methods,contributing to ongoing efforts in environmental management.
基金supported by the National Natural Science Foundation of China(Nos.72349001 and 42301333)the National Key Research and Development Program of China(No.2022YFF1301803)。
摘要Over the past five decades,the Research Center for Eco-Environmental Sciences of the Chinese Academy of Sciences(CAS)and its predecessor and associated laboratories—including the Key Laboratory of Systems Ecology of CAS(established in 1986),the State Key Laboratory of Urban and Regional Ecology(established in 2006),and the recently approved State Key Laboratory of Regional and Urban Ecology(2025)—have made seminal contributions to the development and application of the social-economic-natural complex ecosystem(SENCE)theory.Initially proposed in 1984 by Shijun Ma and Rusong Wang,SENCE theory is an interdisciplinary,holistic,and integrative framework for understanding the complex interactions and feedback mechanisms between social,economic,and natural subsystems.SENCE theory has underpinned the development of the pattern–process–service–sustainability(PPSS)research paradigm,which has been used to systematically analyze the dynamics of fragile ecosystems such as the Loess Plateau and to design innovative solutions for ecological restoration and sustainable regional development.The theory has also significantly advanced research in ecosystem services and ecological security,providing the scientific basis for key national initiatives such as ecological function zoning,the ecological conservation redline policy,and the establishment of China's national park system.Furthermore,the development and application of SENCE theory have catalyzed the emergence of urban ecology as a distinct interdisciplinary field in China,exemplified by the establishment of the country's first urban ecosystem research station in Beijing.This station has generated long-term ecological data on,novel theoretical insights into,and practical policy support for sustainable urban planning and management.In addition,grounded in SENCE theory,a series of pioneering sustainability models have been developed and implemented,including China's first“ecological province”(Hainan),“ecological city”(Yangzhou),“ecological county”(Dafeng),and the first national pilot program for realizing the value of ecological products(Lishui).These models have shown how the SENCE approach can effectively bridge ecological conservation and socio-economic development,providing practical pathways for regional sustainability.Looking ahead,SENCE research will continue to advance theoretical understanding,enhance computational modeling and simulation capabilities,and strengthen evidence-based policy-making.By aligning with China's national ecological civilization strategy as well as global sustainability agendas,future research within this framework will not only inform the construction of a“Beautiful China”but also contribute Chinese wisdom and solutions to global ecological governance.
基金financially supported by the Beijing Natural Science Foundation(No.2232019)National Natural Science Foundation of China(Nos.22373113,22033005,22250710677,and 22303037)+1 种基金NSFC Center for Single-Atom Catalysis(22388102)the Fundamental Research Funds for the Central Universities(No.2023ZKPYHH01).
摘要The conversion of molecular dinitrogen(N2)into ammonia(NH3)is one of the most important chemical pro-cesses.The hemilabile axial bonding in the transition metal(TM)complexes with d-p,d-d and d-df interactions could provide an electron reservoir that controls the evolution of the oxidation state on the active center,which is potential to facilitate N2-to-NH3 conversion.In this perspective,the bionic nitrogen fixing process is illustrated on a molecular level,which features flexible axial bonding to regulate"electron reservoir".The comprehensive overview summarizes the features of TM complexes with axial supporting ligand and focuses on how the axial"assistant"atom tunes the electronic properties of the metal center to facilitate dinitrogen binding,as well as proton/electron delivery in N2 reduction.To illustrate the mechanism of axial"electron reservoir"in dinitrogen fixation on different TM complexes with axial supporting ligand,the relationships of geometric parameters,the variation of electronic structure and oxidation state,the influence principles of axial bonding regulated by an-chor atoms,the critical roles of peripheral ligands and the overall comprehension from orbital interaction are all involved.A preliminary view of the major challenges and future opportunities of TM dinitrogen complexes with flexible axial bonding is highlighted at the end.Through this perspective,we hope to give a comprehensive demonstration of the flexible axial bonding as"electron reservoir"in dinitrogen fixation,and shed light on the rational design for fabricating efficient catalysts in the future.
摘要To investigate the antitumor properties of copper(Ⅱ)complexes,a series of Cucomplexes(C1-C3)derived from 6,7-dihydro-5H-quinoline-8-one thiosemicarbazone ligands was designed and synthesized.These complexes exhibited significantly higher potency in inhibiting tumor cell growth in vitro compared to cisplatin.Among them,C3 had the highest antitumor activity against MDA-MB-231 cells,with a half maximal inhibitory concentration(IC50)value of 1.42μmol·L-1.Moreover,C3 effectively inhibited the growth of 3D multicellular spheres.Mechanistically,it induced significant reactive oxygen species(ROS)generation,initiating a dual-pathway cytotoxic effect.On the one hand,it triggers endoplasmic reticulum stress and inhibits the activity of the related protein,protein disulfide isomerase(PDI).On the other hand,it induces mitochondrial dysfunction.These combined stresses ultimately lead to the apoptosis of MDA-MB-231 cells.
摘要To develop highly stable and active Ru complex catalysts for CO2hydrogenation,we synthesized Ru complexes bearing rigid pincer-type tridentate NNN(pyrazole-pyridine-pyrazole)ligands and weakly coordinated triphenylphosphine(PPh3)ligands.The NNN ligands can strongly chelate with the Ru metal center,contributing to the overall robustness of the catalytic system.Meanwhile,PPh3 can easily dissociate to form vacant coordination sites,thereby enhancing catalytic activity.As a result,the Ru-NNN complex[Ru(L-NNN)Cl(PPh3)2]Cl(1,L-NNN=2,6bis(5-methyl-1H-pyrazol-3-yl)pyridine)was not only quite stable,but also showed high activity for CO2hydrogenation to formate,achieving a TON of up to 150000.In the mechanism study,based on the results of in-situ NMR,in-situ HPLC-HRMS spectra,and density functional theory calculations,it is speculated that the active intermediates with empty coordination sites are highly active species in CO2hydrogenation.
基金supported by the National Natural Science Foundation of China(22571149,22273036,22025101,22222103)。
摘要Symmetry-breaking structural phase transitions in spin crossover(SCO)complexes play a pivotal role in the development of multifunctional SCO materials.In this work,the influence of counter anions on the symmetry-breaking behavior and SCO properties was investigated in three mononuclear FeⅢ-qsal type complexes,[Fe(qsal-4-Me)2]A(Hqsal-4-Me=4-methyl-N-(8-quinolyl)salicylaldimine;A=BF4-(1_(BF4)),ClO4-(2_(ClO4)),and OTf-(3OTf)).All complexes exhibit a typical"Chain-Layer"structural motif.Single-crystal structural analysis at varying temperatures(50-400 K for 1_(BF4) and 120-300 K for 2_(ClO4))revealed distinct symmetry-breaking behaviors in 1_(BF4) and 2_(ClO4).Notably,1_(BF4) undergoes complete symmetry-breaking and re-entrant behavior,coupled with a three-step SCO,while 2_(ClO4) shows only symmetry-breaking incomplete SCO without re-entrance.Structure analyses indicated that the more compact crystal packing in 2_(ClO4)strengthens the elastic interactions between the high-spin FeⅢcenters.This stabilizes the low-spin/high-spin[LS-HS]intermediate phase,thereby inhibiting the reentrant behavior.Compound 3OTf with the largest OTf-anion remains in the HS state below 400 K.While 1_(BF4) showed no LIESST effect,2_(ClO4) displayed a rare reverse-LIESST effect upon irradiation with 980 nm light.The findings reported here demonstrate that subtle variations in anion type can dramatically modulate SCO behavior,offering valuable insights for the design of functional materials with tailored spin transitions.