A visible-light induced cascade sulfonation/cyclization reaction of 3-allyl-2-arylquinazolinones employing water as an environmentally friendly solvent was revealed.This transition metal-free protocol,using 9-mesityl-...A visible-light induced cascade sulfonation/cyclization reaction of 3-allyl-2-arylquinazolinones employing water as an environmentally friendly solvent was revealed.This transition metal-free protocol,using 9-mesityl-10-methylacridinium perchlorate as the photocatalyst,represents a masterly tactic for the synthesis of sulfonated dihydroisoquinolino[1,2-b]quinazolinones featuring mild conditions,facile operation,and broad substrate scope.展开更多
Mangicol-type sesterterpenoids possess potent anti-inflammatory activity,characterized by a 5-5-6-5tetracyclic carbon skeleton formed by mangicdiene synthase Fg MS.Two proposed mechanisms for mangicdiene formation inv...Mangicol-type sesterterpenoids possess potent anti-inflammatory activity,characterized by a 5-5-6-5tetracyclic carbon skeleton formed by mangicdiene synthase Fg MS.Two proposed mechanisms for mangicdiene formation involve either C6-C10 cyclization(path a) or C2-C10 cyclization(path b) after the C10carbocation formation,but neither has been experimentally validated.Here,we have identified a second mangicdiene synthase Man D,which is derived from Fusarium sp.JNU-XJ070152-01 and shares high amino acid sequence identity with Fg MS.Through heterologous expression of man D in Aspergillus oryzae NSAR1,we observed production not only of mangicdiene(1) and variecoltetraene(2),previously identified by expression of Fg MS in Escherichia coli,but also two novel sesterterpene skeletons fusadiene(3)and fusatriene(4).The identification of fusadiene and fusatriene supports the occurrence of two key carbocation intermediates in path b,thus experimentally confirming that mangicdiene is built via path b for the first time,consistent with previous density functional theory(DFT) calculation results.展开更多
Biomass-derived carbon materials are favored for their abundance and sustainability,and ease of preparation and modification.By surface activation and modification they can have a good electrical conductivity,excellen...Biomass-derived carbon materials are favored for their abundance and sustainability,and ease of preparation and modification.By surface activation and modification they can have a good electrical conductivity,excellent catalytic activity,a remarkable adsorption capacity,and different interfacial physicochemical functionalities.Surface-modified biochars have found wide applications in energy storage,environmental remediation,and catalysis.However,achieving precise and controllable modification of their active sites remains a challenge.Recent advances and future prospects for controlling their surface morphology,defect engineering,and surface coating strategies,with particular attention to their means of fabrication,are reviewed.展开更多
Rationale:This case report describes a couple with recurrent fertilization failure despite undergoing multiple cycles of intracytoplasmic sperm injection(ICSI).The principal clinical concern was suspected oocyte activ...Rationale:This case report describes a couple with recurrent fertilization failure despite undergoing multiple cycles of intracytoplasmic sperm injection(ICSI).The principal clinical concern was suspected oocyte activation deficiency(OAD),in which fertilization is impeded due to the oocyte’s inability to initiate embryogenesis,commonly attributed to inadequate intracellular calcium(Ca^(2+))release following sperm injection.Patient concerns:The couple repeatedly experienced complete or near-complete fertilization failure in previous ICSI cycles,raising suspicion of an underlying oocyte activation defect.Diagnosis:Based on the repeated absence of fertilization post-ICSI and clinical history,a diagnosis of suspected OAD leading to recurrent ICSI fertilization failure was considered.Interventions:Artificial oocyte activation(AOA)using the calcium ionophore A23187 was performed.After ICSI,unfertilized oocytes were exposed to the ionophore to induce Ca^(2+)influx,simulating physiological calcium oscillations essential for oocyte activation.The efficacy of intervention was evaluated through subsequent embryonic development,morphological grading,and chromosomal integrity.Outcomes:Following AOA treatment,successful oocyte activation occurred,resulting in the formation of high-grade embryos with normal developmental progression.Chromosomal analysis revealed no detectable abnormalities,indicating genomic stability.Lessons:Calcium ionophore–mediated AOA may serve as an effective adjunct in cases of recurrent ICSI failure attributed to OAD.This case highlights the importance of individualized therapeutic strategies in assisted reproduction;however,further research is needed to refine protocols,validate broader clinical efficacy,and assess long-term safety,including potential epigenetic risks.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
Activation pruning reduces neural network complexity by eliminating low-importance neuron activations,yet identifying the critical pruning threshold—beyond which accuracy rapidly deteriorates—remains computationally...Activation pruning reduces neural network complexity by eliminating low-importance neuron activations,yet identifying the critical pruning threshold—beyond which accuracy rapidly deteriorates—remains computationally expensive and typically requires exhaustive search.We introduce a thermodynamics-inspired framework that treats activation distributions as energy-filtered physical systems and employs the free energy of activations as a principled evaluation metric.Phase-transition-like phenomena in the free-energy profile—such as extrema,inflection points,and curvature changes—yield reliable estimates of the critical pruning threshold,providing a theoretically grounded means of predicting sharp accuracy degradation.To further enhance efficiency,we propose a renormalized free energy technique that approximates full-evaluation free energy using only the activation distribution of the unpruned network.This eliminates repeated forward passes,dramatically reducing computational overhead and achieving speedups of up to 550×for MLPs.Extensive experiments across diverse vision architectures(MLP,CNN,ResNet,MobileNet,Vision Transformer)and text models(LSTM,BERT,ELECTRA,T5,GPT-2)on multiple datasets validate the generality,robustness,and computational efficiency of our approach.Overall,this work establishes a theoretically grounded and practically effective framework for activation pruning,bridging the gap between analytical understanding and efficient deployment of sparse neural networks.展开更多
Peroxymonosulfate(PMS)-assisted visible-light photocatalytic degradation of organic pollutants using graphitic carbon nitride(g-C_(3)N_(4))presents a promising and environmentally friendly approach.However,pristine g-...Peroxymonosulfate(PMS)-assisted visible-light photocatalytic degradation of organic pollutants using graphitic carbon nitride(g-C_(3)N_(4))presents a promising and environmentally friendly approach.However,pristine g-C_(3)N_(4) suffers from limited visible-light absorption and low charge-carrier mobility.In this study,a phosphorus-doped tubular carbon nitride(5P-TCN)was synthesized via a precursor self-assembly method using phosphoric acid and melamine as raw materials,eliminating the need for organic solvents or templates.The 5P-TCN catalyst demonstrated enhanced visible-light absorption,improved charge transfer capability,and a 5.25-fold increase in specific surface area(31.092 m^(2)/g),which provided abundant active sites to efficiently drive the PMS-assisted photocatalytic reaction.The 5P-TCN/vis/PMS system exhibited exceptional degradation performance for organic pollutants across a broad pH range(3–9),achieving over 92%degradation of Rhodamine B(RhB)within 15 min.Notably,the system retained>98%RhB degradation efficiency after three consecutive operational cycles,demonstrating robust operational stability and reusability.Moreover,key parameters influencing,active radi-cals,degradation pathways,and potential mechanisms for RhB degradation were systematically investigated.This work proposes a green and cost-effective strategy for developing high-efficiency photocatalysts,while demon-strating the exceptional capability of a PMS-assisted photocatalytic system for rapid degradation of RhB.展开更多
Mammalian fertilization involves the migration of spermatozoa through the female reproductive system.Early embryonic development is a consequence of several steps and signaling pathways being activated,as well as bioc...Mammalian fertilization involves the migration of spermatozoa through the female reproductive system.Early embryonic development is a consequence of several steps and signaling pathways being activated,as well as biochemical and morphological modifications of spermatozoa that enable them to penetrate the membrane of mature oocytes.There are some crucial steps known to clearly explain the process of fertilization,starting with hyperactivation of spermatozoa,mutual recognition,and binding of gametes mediated by receptors located on the surface membranes of both gametes.The final step is followed by oocyte activation,which is primarily triggered via sperm-derived factors,inducing a sharp increase in intracellular calcium levels,eventually leading to polyspermy block.This review integrates current knowledge of the molecular and physiological events governing fertilization,emphasizing how ion regulation and signaling pathways converge to enable sperm function and oocyte activation.Special attention is given to sperm-derived factors such as phospholipase C zeta(PLCζ)and post-acrosomal sheath WW domain-binding protein(PAWP),which play essential roles in triggering calcium release and supporting early embryonic development.展开更多
Given that platinum-based drugs are widely used clinically as chemotherapeutic agents,their severe toxic side effects have attracted significant attention.Consequently,the development of novel nanoprodrugs based on lo...Given that platinum-based drugs are widely used clinically as chemotherapeutic agents,their severe toxic side effects have attracted significant attention.Consequently,the development of novel nanoprodrugs based on low-toxicity tetravalent platinum(Pt(Ⅳ))com plexes holds substantial research value.Herein,we discovered that coumarin derivatives exhibit inherent antitumor efficacy and significantly enhance superoxide anion radicals(·O_(2)^(-))generation in aqueous solutions under ultrasound(US)irradiation.Given that·O_(2)^(-)is known to mediate the reduction of Pt(Ⅳ)to divalent platinum(Pt(Ⅱ)),we engineered an US-responsive dual-drug nanoprodrug(P-cisPt(Ⅳ)@5-MOP).This nanoprodrug was prepared by covalently conjugating Pt(Ⅳ)and methoxy polyethylene glycol hydroxyl(m PEG-OH)to a poly(_(L)-glutamic acid)(PLG)carrier,followed by encapsulating coumarin derivatives.Under low-intensity US irradiation(1.5 W/cm^(2),1 MHz,10 min),P-cisPt(Ⅳ)@5-MOP achieved a Pt(Ⅳ)reduction rate of 91.4%.Furthermore,upon US exposure,its half-maximal inhibitory concentration(IC_(50))against 4T1 breast cancer cells decreased dramatically from 25.7μmol/L to 0.1μmol/L.Remarkably,this system combined with US therapy yielded a tumor inhibition rate of 90.9%,with 40%of tumor-bea ring mice achieving com plete eradication of tumors,while exhibiting low systemic toxicity.Collectively,this work not only identifies a novel sonosensitizer capable of generating·O_(2)^(-)but also develops a new class of ultrasound-activatable Pt(Ⅳ)nanoprodrug.展开更多
Machine learning(ML)is recognized as a potent tool for the inverse design of environmental functional material,particularly for complex entities like biochar-based catalysts(BCs).Thus,the tailored BCs can have a disti...Machine learning(ML)is recognized as a potent tool for the inverse design of environmental functional material,particularly for complex entities like biochar-based catalysts(BCs).Thus,the tailored BCs can have a distinct ability to trigger the nonradical pathway in advance oxidation processes(AOPs),promising a stable,rapid and selective degradation of persistent contaminants.However,due to the inherent“black box”nature and limitations of input features,results and conclusions derived from ML may not always be intuitively understood or comprehensively validated.To tackle this challenge,we linked the front-point interpretable analysis approaches with back-point density functional theory(DFT)calculations to form a chained learning strategy for deeper sight into the intrinsic activation mechanism of BCs in AOPs.At the front point,we conducted an easy-to-interpret meta-analysis to validate two strategies for enhancing nonradical pathways by increasing oxygen content and specific surface area(SSA),and prepared oxidized biochar(OBC500)and SSA-increased biochar(SBC900)by controlling pyrolysis conditions and modification methods.Subsequently,experimental results showed that OBC500 and SBC900 had distinct dominant degradation pathways for 1O2 generation and electron transfer,respectively.Finally,at the end point,DFT calculations revealed their active sites and degradation mechanisms.This chained learning strategy elucidates fundamental principles for BC inverse design and showcases the exceptional capacity to integrate computational techniques to accelerate catalyst inverse design.展开更多
In image analysis,high-precision semantic segmentation predominantly relies on supervised learning.Despite significant advancements driven by deep learning techniques,challenges such as class imbalance and dynamic per...In image analysis,high-precision semantic segmentation predominantly relies on supervised learning.Despite significant advancements driven by deep learning techniques,challenges such as class imbalance and dynamic performance evaluation persist.Traditional weighting methods,often based on pre-statistical class counting,tend to overemphasize certain classes while neglecting others,particularly rare sample categories.Approaches like focal loss and other rare-sample segmentation techniques introduce multiple hyperparameters that require manual tuning,leading to increased experimental costs due to their instability.This paper proposes a novel CAWASeg framework to address these limitations.Our approach leverages Grad-CAM technology to generate class activation maps,identifying key feature regions that the model focuses on during decision-making.We introduce a Comprehensive Segmentation Performance Score(CSPS)to dynamically evaluate model performance by converting these activation maps into pseudo mask and comparing them with Ground Truth.Additionally,we design two adaptive weights for each class:a Basic Weight(BW)and a Ratio Weight(RW),which the model adjusts during training based on real-time feedback.Extensive experiments on the COCO-Stuff,CityScapes,and ADE20k datasets demonstrate that our CAWASeg framework significantly improves segmentation performance for rare sample categories while enhancing overall segmentation accuracy.The proposed method offers a robust and efficient solution for addressing class imbalance in semantic segmentation tasks.展开更多
Most Convolutional Neural Network(CNN)interpretation techniques visualize only the dominant cues that the model relies on,but there is no guarantee that these represent all the evidence the model uses for classificati...Most Convolutional Neural Network(CNN)interpretation techniques visualize only the dominant cues that the model relies on,but there is no guarantee that these represent all the evidence the model uses for classification.This limitation becomes critical when hidden secondary cues—potentially more meaningful than the visualized ones—remain undiscovered.This study introduces CasCAM(Cascaded Class Activation Mapping)to address this fundamental limitation through counterfactual reasoning.By asking“if this dominant cue were absent,what other evidence would the model use?”,CasCAM progressively masks the most salient features and systematically uncovers the hierarchy of classification evidence hidden beneath them.Experimental results demonstrate that CasCAM effectively discovers the full spectrum of reasoning evidence and can be universally applied with nine existing interpretation methods.展开更多
Triclosan(TCS) poses harmful risks to ecosystems and human health owing to its endocrine-disrupting effects.Therefore,developing an efficient and sustainable technology to degrade TCS is urgently needed.Herein,cobalt ...Triclosan(TCS) poses harmful risks to ecosystems and human health owing to its endocrine-disrupting effects.Therefore,developing an efficient and sustainable technology to degrade TCS is urgently needed.Herein,cobalt oxyhydroxide @covalent organic frameworks(CoOOH@COFs) S-scheme heterojunction was synthesized,which combined the visible-light-driven photocatalysis and peroxymonosulfate(PMS) activation to synergistically generate abundant reactive oxygen species(ROSs) for TCS degradation.The degradation efficiency of TCS reached 100 % within 8 min in the Vis-CoOOH@COFs/PMS system,and the reaction rate constant was 0.456 min^(-1),which was nearly 1.90 and 2.85 times that of single Co OOH and COFs,and2.36 times that under dark condition,respectively.The density functional theory(DFT) calculations confirmed the energy band bending of CoOOH@COFs and S-scheme charge transport from COFs to Co OOH.Both experimental and theoretical analyses indicated that Co OOH@COFs in photocatalytic-PMS activation systems synergistically facilitated photo-generated carrier separation,enhanced interfacial electron transfer,accelerated PMS activation,and generated multiple ROSs.In particular,photogenerated electrons(e^(-))accelerated the Co(Ⅲ)/Co(Ⅱ) redox cycle,while the PMS captured the e-,which significantly decreased the charge combination of Co OOH@COFs.Radicals(O_(2)^(·-),^(·)OH,and SO_(4)^(·-)) and non-radicals(such as ^(1)O_(2),h^(+),and e^(-)) were both presented in the Vis-CoOOH@COFs/PMS system,with O_(2)^(-) playing a dominant role in TCS degradation.Furthermore,the pathway of TCS degradation and toxicity of intermediates were explored by DFT calculation and transformation product identification.Importantly,the environmentally friendly CoOOH@COFs S-scheme heterojunction exhibited excellent stability and reusability.In conclusion,this study innovatively designed an S-scheme heterojunction in the photocatalytic-PMS activation system,providing guidance and theoretical support for efficient and eco-friendly wastewater treatment.展开更多
The accumulation of refractory organics in Bayer liquor(pH 14.4)critically compromises aluminum production efficiency and product quality,necessitating sustainable remediation strategies.Herein,we develop an ultrasoni...The accumulation of refractory organics in Bayer liquor(pH 14.4)critically compromises aluminum production efficiency and product quality,necessitating sustainable remediation strategies.Herein,we develop an ultrasonic-driven catalytic ozonation system with dynamically reconstructed CuO/Cu2O heterointerfaces,achieving unprecedented efficiency in extreme alkaline wastewater treatment.Atomic-scale interface engineering endows the catalyst with hydrophilicity(contact angle:6.1°)and 3.8–4.3 times higher oxygen vacancy density compared to single-phase catalysts.These properties facilitate efficient interfacial interactions with Bayer liquor and enable superior ozone activation through synergistic Cu(I)/Cu(II)redox cycling across the heterointerface.This interfacial synergy reduces ozone adsorption energy from 5.46 eV(Cu_(2)O)to 1.48 eV,driving the generation of reactive oxygen species(ROS)via low-energy pathways.Under optimized conditions,the system achieves 57.82%TOC removal within 1.5 h with 2.3-fold faster kinetics than ozone–alone processes,while improving energy efficiency by 1.82–3.22 times per kWh over conventional thermal oxidation.Remarkable stability is demonstrated through 80.21%activity retention after 6 cycles,attributed to surface energy minimization(0.61 J m^(−2)),alongside 67.91%hydroxyl radical(•OH)-mediated degradation confirmed by quenching tests.In XPS,EEMs analysis,and ECOSAR modeling further elucidate the surface reconstruction mechanism and intermediate toxicity reduction.This work establishes an atomic interface design paradigm that bridges catalytic innovation with green metallurgy applications,offering a sustainable solution for industrial wastewater remediation aligned with circular economy principles.展开更多
The dissolution of iron from the cathode and electrode/electrolyte interface(EEI)during long cycles significantly accelerates the aging process of LiFePO_(4)(LFP)/graphite batteries;there is a lack of systematic under...The dissolution of iron from the cathode and electrode/electrolyte interface(EEI)during long cycles significantly accelerates the aging process of LiFePO_(4)(LFP)/graphite batteries;there is a lack of systematic understanding of the spatial distribution of the EEI interface layer and the dissolve of Fe ions,especially in terms of the mechanism of the cathode-electrolyte interphase(CEI),solid electrolyte interphase(SEI),and iron dissolution.In this study,aged cells were subjected to continuous activation with constant current and multi-step segmented indirect activation(IA)and analyzed for capacity fade,impedance growth,and active Li^(+)mass loss at the EEI and nanoscale levels.The interaction between dissolved Fe^(2+)and the EEI in LFP/graphite pouch batteries was proposed and verified.The findings indicate that during IA process,the electric field facilitates the migration of solvated ions toward the electrodes,while simultaneously inhibiting the formation of organic species such as ROCO_(2)Li.The SEI primarily consists of a mixture of organic and inorganic small molecules,forming a continuous and uniform film on the electrode surface.This study demonstrates that IA favors the formation of a uniform EEI and offers constructive insights for advancing accelerated lifetime prediction strategies in lithium-ion batteries.展开更多
Cells of the central nervous system(CNS)are privileged in lying behind the blood-brain barrier(BBB).Unlike blood vessels in other organs,CNS blood vessels are unique in displaying high electrical resistance and low pe...Cells of the central nervous system(CNS)are privileged in lying behind the blood-brain barrier(BBB).Unlike blood vessels in other organs,CNS blood vessels are unique in displaying high electrical resistance and low permeability.With this unique structure and function,the BBB prevents potentially harmful blood components such as serum proteins,inflammatory cytokines,and inflammatory leukocytes from entering the hallowed space of the CNS and wreaking havoc.In addition to these“tightness”properties,the BBB has an array of specialized transporters designed to import essential nutrients.展开更多
The functional properties of glasses are governed by their formation history and the complex relaxation processes they undergo.However,under extreme conditions,glass behaviors are still elusive.In this study,we employ...The functional properties of glasses are governed by their formation history and the complex relaxation processes they undergo.However,under extreme conditions,glass behaviors are still elusive.In this study,we employ simulations with varied protocols to evaluate the effectiveness of different descriptors in predicting mechanical properties across both low-and high-pressure regimes.Our findings demonstrate that conventional structural and configurational descriptors fail to correlate with the mechanical response following pressure release,whereas the activation energy descriptor exhibits robust linearity with shear modulus after correcting for pressure effects.Notably,the soft mode parameter emerges as an ideal and computationally efficient alternative for capturing this mechanical behavior.These findings provide critical insights into the influence of pressure on glassy properties,integrating the distinct features of compressed glasses into a unified theoretical framework.展开更多
Disclosed herein is a novel Rh/Ag co-catalyzed S=NH directed C–H activation and C–H/N–H bond functionalization protocol of free NH-sulfoximines with hypervalent iodonium ylides.With the aid of AgOTf,these C–H func...Disclosed herein is a novel Rh/Ag co-catalyzed S=NH directed C–H activation and C–H/N–H bond functionalization protocol of free NH-sulfoximines with hypervalent iodonium ylides.With the aid of AgOTf,these C–H functionalization/cyclization sequences could be achieved at room temperature conditions.The reaction employed EtOH as a“green”solvent and low catalyst loading was required under an oxygen/water-insensitive condition.Under this mild protocol,a wide range of polyheterocyclic sulfoximines bearing fused saturated carbo(hetero)cycles are readily prepared,even toward a complex pharmaceutical Folliculin analog.展开更多
The development of enantioselective C-H macrocyclizations to efficiently access structurally diversified macrocycles is highly desirable,but remain a big challenge.Herein,we reported the first rhodium(Ⅲ)-catalyzed as...The development of enantioselective C-H macrocyclizations to efficiently access structurally diversified macrocycles is highly desirable,but remain a big challenge.Herein,we reported the first rhodium(Ⅲ)-catalyzed asymmetric intramolecular C-H macrocyclization,enabling the efficient synthesis of structurally diverse enantioenriched macrocycles.This robust enantioselective C-H macrocyclization has a broad functional group tolerance,excellent enantioselectivities(up to 98.5:1.5 e.r.)and a mild reaction condition,releasing CO_(2)as the single by-product.More significantly,the resulting unique enantioenriched19-membered macrocycle 2f was found to demonstrate a potent in vitro anti-Zika virus(ZIKV)activity without obvious cytotoxicity.Further investigation revealed that the anti-ZIKV activity is presumably attributed to an autophagy inhibition in the early stage of viral infection by down-regulating the expression of autophagy related gene Atg12.展开更多
基金funds from Natural Science Foundation of Guangxi Province(Nos.2023GXNSFBA026304,2023GXNSFDA026063)the Guangxi Science and Technology Base and Special Talents(No.Guike AD20159047).
文摘A visible-light induced cascade sulfonation/cyclization reaction of 3-allyl-2-arylquinazolinones employing water as an environmentally friendly solvent was revealed.This transition metal-free protocol,using 9-mesityl-10-methylacridinium perchlorate as the photocatalyst,represents a masterly tactic for the synthesis of sulfonated dihydroisoquinolino[1,2-b]quinazolinones featuring mild conditions,facile operation,and broad substrate scope.
基金financially supported by grants from the National Key Research and Development Program of China (No.2024YFE0102000)the National Natural Science Foundation of China (Nos.81925037,82321004,U22A20371,U24A20782,32170060,22177037,22207039,22307045)+6 种基金the Guangdong Major Project of Basic and Applied Basic Research (No.2023B0303000026)the Guangdong Natural Science Funds for Distinguished Young Scholars (No.2022B1515020028,China)the Guangdong International Science and Technology Cooperation Base (No.2021A0505020015,China)the Guangdong Basic and Applied Basic Research Foundation (Nos.2023B1515040016,2023A1515110388)the Innovative and Research Teams Project of Guangdong Higher Education Institution (No.2021KCXTD001,China)the Guangzhou Science and Technology Project (Nos.202206010020,2024A04J6241,2023A04J0080,China)the Fundamental Research Funds for the Central Universities (Nos.21623105,21624210)。
文摘Mangicol-type sesterterpenoids possess potent anti-inflammatory activity,characterized by a 5-5-6-5tetracyclic carbon skeleton formed by mangicdiene synthase Fg MS.Two proposed mechanisms for mangicdiene formation involve either C6-C10 cyclization(path a) or C2-C10 cyclization(path b) after the C10carbocation formation,but neither has been experimentally validated.Here,we have identified a second mangicdiene synthase Man D,which is derived from Fusarium sp.JNU-XJ070152-01 and shares high amino acid sequence identity with Fg MS.Through heterologous expression of man D in Aspergillus oryzae NSAR1,we observed production not only of mangicdiene(1) and variecoltetraene(2),previously identified by expression of Fg MS in Escherichia coli,but also two novel sesterterpene skeletons fusadiene(3)and fusatriene(4).The identification of fusadiene and fusatriene supports the occurrence of two key carbocation intermediates in path b,thus experimentally confirming that mangicdiene is built via path b for the first time,consistent with previous density functional theory(DFT) calculation results.
文摘Biomass-derived carbon materials are favored for their abundance and sustainability,and ease of preparation and modification.By surface activation and modification they can have a good electrical conductivity,excellent catalytic activity,a remarkable adsorption capacity,and different interfacial physicochemical functionalities.Surface-modified biochars have found wide applications in energy storage,environmental remediation,and catalysis.However,achieving precise and controllable modification of their active sites remains a challenge.Recent advances and future prospects for controlling their surface morphology,defect engineering,and surface coating strategies,with particular attention to their means of fabrication,are reviewed.
文摘Rationale:This case report describes a couple with recurrent fertilization failure despite undergoing multiple cycles of intracytoplasmic sperm injection(ICSI).The principal clinical concern was suspected oocyte activation deficiency(OAD),in which fertilization is impeded due to the oocyte’s inability to initiate embryogenesis,commonly attributed to inadequate intracellular calcium(Ca^(2+))release following sperm injection.Patient concerns:The couple repeatedly experienced complete or near-complete fertilization failure in previous ICSI cycles,raising suspicion of an underlying oocyte activation defect.Diagnosis:Based on the repeated absence of fertilization post-ICSI and clinical history,a diagnosis of suspected OAD leading to recurrent ICSI fertilization failure was considered.Interventions:Artificial oocyte activation(AOA)using the calcium ionophore A23187 was performed.After ICSI,unfertilized oocytes were exposed to the ionophore to induce Ca^(2+)influx,simulating physiological calcium oscillations essential for oocyte activation.The efficacy of intervention was evaluated through subsequent embryonic development,morphological grading,and chromosomal integrity.Outcomes:Following AOA treatment,successful oocyte activation occurred,resulting in the formation of high-grade embryos with normal developmental progression.Chromosomal analysis revealed no detectable abnormalities,indicating genomic stability.Lessons:Calcium ionophore–mediated AOA may serve as an effective adjunct in cases of recurrent ICSI failure attributed to OAD.This case highlights the importance of individualized therapeutic strategies in assisted reproduction;however,further research is needed to refine protocols,validate broader clinical efficacy,and assess long-term safety,including potential epigenetic risks.
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output of a research project implemented as part of the Basic Research Program at HSE University。
文摘Activation pruning reduces neural network complexity by eliminating low-importance neuron activations,yet identifying the critical pruning threshold—beyond which accuracy rapidly deteriorates—remains computationally expensive and typically requires exhaustive search.We introduce a thermodynamics-inspired framework that treats activation distributions as energy-filtered physical systems and employs the free energy of activations as a principled evaluation metric.Phase-transition-like phenomena in the free-energy profile—such as extrema,inflection points,and curvature changes—yield reliable estimates of the critical pruning threshold,providing a theoretically grounded means of predicting sharp accuracy degradation.To further enhance efficiency,we propose a renormalized free energy technique that approximates full-evaluation free energy using only the activation distribution of the unpruned network.This eliminates repeated forward passes,dramatically reducing computational overhead and achieving speedups of up to 550×for MLPs.Extensive experiments across diverse vision architectures(MLP,CNN,ResNet,MobileNet,Vision Transformer)and text models(LSTM,BERT,ELECTRA,T5,GPT-2)on multiple datasets validate the generality,robustness,and computational efficiency of our approach.Overall,this work establishes a theoretically grounded and practically effective framework for activation pruning,bridging the gap between analytical understanding and efficient deployment of sparse neural networks.
文摘Peroxymonosulfate(PMS)-assisted visible-light photocatalytic degradation of organic pollutants using graphitic carbon nitride(g-C_(3)N_(4))presents a promising and environmentally friendly approach.However,pristine g-C_(3)N_(4) suffers from limited visible-light absorption and low charge-carrier mobility.In this study,a phosphorus-doped tubular carbon nitride(5P-TCN)was synthesized via a precursor self-assembly method using phosphoric acid and melamine as raw materials,eliminating the need for organic solvents or templates.The 5P-TCN catalyst demonstrated enhanced visible-light absorption,improved charge transfer capability,and a 5.25-fold increase in specific surface area(31.092 m^(2)/g),which provided abundant active sites to efficiently drive the PMS-assisted photocatalytic reaction.The 5P-TCN/vis/PMS system exhibited exceptional degradation performance for organic pollutants across a broad pH range(3–9),achieving over 92%degradation of Rhodamine B(RhB)within 15 min.Notably,the system retained>98%RhB degradation efficiency after three consecutive operational cycles,demonstrating robust operational stability and reusability.Moreover,key parameters influencing,active radi-cals,degradation pathways,and potential mechanisms for RhB degradation were systematically investigated.This work proposes a green and cost-effective strategy for developing high-efficiency photocatalysts,while demon-strating the exceptional capability of a PMS-assisted photocatalytic system for rapid degradation of RhB.
文摘Mammalian fertilization involves the migration of spermatozoa through the female reproductive system.Early embryonic development is a consequence of several steps and signaling pathways being activated,as well as biochemical and morphological modifications of spermatozoa that enable them to penetrate the membrane of mature oocytes.There are some crucial steps known to clearly explain the process of fertilization,starting with hyperactivation of spermatozoa,mutual recognition,and binding of gametes mediated by receptors located on the surface membranes of both gametes.The final step is followed by oocyte activation,which is primarily triggered via sperm-derived factors,inducing a sharp increase in intracellular calcium levels,eventually leading to polyspermy block.This review integrates current knowledge of the molecular and physiological events governing fertilization,emphasizing how ion regulation and signaling pathways converge to enable sperm function and oocyte activation.Special attention is given to sperm-derived factors such as phospholipase C zeta(PLCζ)and post-acrosomal sheath WW domain-binding protein(PAWP),which play essential roles in triggering calcium release and supporting early embryonic development.
基金financially supported by the National Natural Science Foundation of China(Nos.52533015,52495013,52403211,52573183,52273157,52073279 and 52025035)Jilin Province,China(Nos.20250601009RC and 20230508102RC)Youth Innovation Promotion Association of the Chinese Academy of Sciences(No.2022224)。
文摘Given that platinum-based drugs are widely used clinically as chemotherapeutic agents,their severe toxic side effects have attracted significant attention.Consequently,the development of novel nanoprodrugs based on low-toxicity tetravalent platinum(Pt(Ⅳ))com plexes holds substantial research value.Herein,we discovered that coumarin derivatives exhibit inherent antitumor efficacy and significantly enhance superoxide anion radicals(·O_(2)^(-))generation in aqueous solutions under ultrasound(US)irradiation.Given that·O_(2)^(-)is known to mediate the reduction of Pt(Ⅳ)to divalent platinum(Pt(Ⅱ)),we engineered an US-responsive dual-drug nanoprodrug(P-cisPt(Ⅳ)@5-MOP).This nanoprodrug was prepared by covalently conjugating Pt(Ⅳ)and methoxy polyethylene glycol hydroxyl(m PEG-OH)to a poly(_(L)-glutamic acid)(PLG)carrier,followed by encapsulating coumarin derivatives.Under low-intensity US irradiation(1.5 W/cm^(2),1 MHz,10 min),P-cisPt(Ⅳ)@5-MOP achieved a Pt(Ⅳ)reduction rate of 91.4%.Furthermore,upon US exposure,its half-maximal inhibitory concentration(IC_(50))against 4T1 breast cancer cells decreased dramatically from 25.7μmol/L to 0.1μmol/L.Remarkably,this system combined with US therapy yielded a tumor inhibition rate of 90.9%,with 40%of tumor-bea ring mice achieving com plete eradication of tumors,while exhibiting low systemic toxicity.Collectively,this work not only identifies a novel sonosensitizer capable of generating·O_(2)^(-)but also develops a new class of ultrasound-activatable Pt(Ⅳ)nanoprodrug.
基金supported by Project of National and Local Joint Engineering Research Center for Biomass Energy Development and Utilization(Harbin Institute of Technology,No.2021A004).
文摘Machine learning(ML)is recognized as a potent tool for the inverse design of environmental functional material,particularly for complex entities like biochar-based catalysts(BCs).Thus,the tailored BCs can have a distinct ability to trigger the nonradical pathway in advance oxidation processes(AOPs),promising a stable,rapid and selective degradation of persistent contaminants.However,due to the inherent“black box”nature and limitations of input features,results and conclusions derived from ML may not always be intuitively understood or comprehensively validated.To tackle this challenge,we linked the front-point interpretable analysis approaches with back-point density functional theory(DFT)calculations to form a chained learning strategy for deeper sight into the intrinsic activation mechanism of BCs in AOPs.At the front point,we conducted an easy-to-interpret meta-analysis to validate two strategies for enhancing nonradical pathways by increasing oxygen content and specific surface area(SSA),and prepared oxidized biochar(OBC500)and SSA-increased biochar(SBC900)by controlling pyrolysis conditions and modification methods.Subsequently,experimental results showed that OBC500 and SBC900 had distinct dominant degradation pathways for 1O2 generation and electron transfer,respectively.Finally,at the end point,DFT calculations revealed their active sites and degradation mechanisms.This chained learning strategy elucidates fundamental principles for BC inverse design and showcases the exceptional capacity to integrate computational techniques to accelerate catalyst inverse design.
基金supported by the Funds for Central-Guided Local Science and Technology Development(Grant No.202407AC110005)Key Technologies for the Construction of a Whole-Process Intelligent Service System for Neuroendocrine Neoplasm.Supported by 2023 Opening Research Fund of Yunnan Key Laboratory of Digital Communications(YNJTKFB-20230686,YNKLDC-KFKT-202304).
文摘In image analysis,high-precision semantic segmentation predominantly relies on supervised learning.Despite significant advancements driven by deep learning techniques,challenges such as class imbalance and dynamic performance evaluation persist.Traditional weighting methods,often based on pre-statistical class counting,tend to overemphasize certain classes while neglecting others,particularly rare sample categories.Approaches like focal loss and other rare-sample segmentation techniques introduce multiple hyperparameters that require manual tuning,leading to increased experimental costs due to their instability.This paper proposes a novel CAWASeg framework to address these limitations.Our approach leverages Grad-CAM technology to generate class activation maps,identifying key feature regions that the model focuses on during decision-making.We introduce a Comprehensive Segmentation Performance Score(CSPS)to dynamically evaluate model performance by converting these activation maps into pseudo mask and comparing them with Ground Truth.Additionally,we design two adaptive weights for each class:a Basic Weight(BW)and a Ratio Weight(RW),which the model adjusts during training based on real-time feedback.Extensive experiments on the COCO-Stuff,CityScapes,and ADE20k datasets demonstrate that our CAWASeg framework significantly improves segmentation performance for rare sample categories while enhancing overall segmentation accuracy.The proposed method offers a robust and efficient solution for addressing class imbalance in semantic segmentation tasks.
基金supported by the Basic Science Research Program through the National Research Foundation of Korea(NRF),funded by the Ministry of Education(RS-2023-00249743).
文摘Most Convolutional Neural Network(CNN)interpretation techniques visualize only the dominant cues that the model relies on,but there is no guarantee that these represent all the evidence the model uses for classification.This limitation becomes critical when hidden secondary cues—potentially more meaningful than the visualized ones—remain undiscovered.This study introduces CasCAM(Cascaded Class Activation Mapping)to address this fundamental limitation through counterfactual reasoning.By asking“if this dominant cue were absent,what other evidence would the model use?”,CasCAM progressively masks the most salient features and systematically uncovers the hierarchy of classification evidence hidden beneath them.Experimental results demonstrate that CasCAM effectively discovers the full spectrum of reasoning evidence and can be universally applied with nine existing interpretation methods.
文摘Triclosan(TCS) poses harmful risks to ecosystems and human health owing to its endocrine-disrupting effects.Therefore,developing an efficient and sustainable technology to degrade TCS is urgently needed.Herein,cobalt oxyhydroxide @covalent organic frameworks(CoOOH@COFs) S-scheme heterojunction was synthesized,which combined the visible-light-driven photocatalysis and peroxymonosulfate(PMS) activation to synergistically generate abundant reactive oxygen species(ROSs) for TCS degradation.The degradation efficiency of TCS reached 100 % within 8 min in the Vis-CoOOH@COFs/PMS system,and the reaction rate constant was 0.456 min^(-1),which was nearly 1.90 and 2.85 times that of single Co OOH and COFs,and2.36 times that under dark condition,respectively.The density functional theory(DFT) calculations confirmed the energy band bending of CoOOH@COFs and S-scheme charge transport from COFs to Co OOH.Both experimental and theoretical analyses indicated that Co OOH@COFs in photocatalytic-PMS activation systems synergistically facilitated photo-generated carrier separation,enhanced interfacial electron transfer,accelerated PMS activation,and generated multiple ROSs.In particular,photogenerated electrons(e^(-))accelerated the Co(Ⅲ)/Co(Ⅱ) redox cycle,while the PMS captured the e-,which significantly decreased the charge combination of Co OOH@COFs.Radicals(O_(2)^(·-),^(·)OH,and SO_(4)^(·-)) and non-radicals(such as ^(1)O_(2),h^(+),and e^(-)) were both presented in the Vis-CoOOH@COFs/PMS system,with O_(2)^(-) playing a dominant role in TCS degradation.Furthermore,the pathway of TCS degradation and toxicity of intermediates were explored by DFT calculation and transformation product identification.Importantly,the environmentally friendly CoOOH@COFs S-scheme heterojunction exhibited excellent stability and reusability.In conclusion,this study innovatively designed an S-scheme heterojunction in the photocatalytic-PMS activation system,providing guidance and theoretical support for efficient and eco-friendly wastewater treatment.
基金supported by Yunnan Major Scientific and Technological Projects(Grant No.202402AB080004)Yunnan Provincial Education Department Universities Serve Key Industry Science and Technology Projects(Grant No:FWCY-BSPY2024043)+1 种基金Top Innovative Talents for Graduate Students of KUST(Grant No:CA24163M116A)Analysis and Testing Fund of KUST(Grant No:2024P20233102006).The authors extend their gratitude to Mr.Kong Qingyuan from Scientific Compass(www.shiyanjia.com)for providing invaluable assistance with scientific research.
文摘The accumulation of refractory organics in Bayer liquor(pH 14.4)critically compromises aluminum production efficiency and product quality,necessitating sustainable remediation strategies.Herein,we develop an ultrasonic-driven catalytic ozonation system with dynamically reconstructed CuO/Cu2O heterointerfaces,achieving unprecedented efficiency in extreme alkaline wastewater treatment.Atomic-scale interface engineering endows the catalyst with hydrophilicity(contact angle:6.1°)and 3.8–4.3 times higher oxygen vacancy density compared to single-phase catalysts.These properties facilitate efficient interfacial interactions with Bayer liquor and enable superior ozone activation through synergistic Cu(I)/Cu(II)redox cycling across the heterointerface.This interfacial synergy reduces ozone adsorption energy from 5.46 eV(Cu_(2)O)to 1.48 eV,driving the generation of reactive oxygen species(ROS)via low-energy pathways.Under optimized conditions,the system achieves 57.82%TOC removal within 1.5 h with 2.3-fold faster kinetics than ozone–alone processes,while improving energy efficiency by 1.82–3.22 times per kWh over conventional thermal oxidation.Remarkable stability is demonstrated through 80.21%activity retention after 6 cycles,attributed to surface energy minimization(0.61 J m^(−2)),alongside 67.91%hydroxyl radical(•OH)-mediated degradation confirmed by quenching tests.In XPS,EEMs analysis,and ECOSAR modeling further elucidate the surface reconstruction mechanism and intermediate toxicity reduction.This work establishes an atomic interface design paradigm that bridges catalytic innovation with green metallurgy applications,offering a sustainable solution for industrial wastewater remediation aligned with circular economy principles.
基金supported by the National Key R&D Program of China(2021YFB2401800)the support from Beijing Nova Program(20230484241)+2 种基金the support from the China Postdoctoral Science Foundation(2024M754084)the Postdoctoral Fellowship Program of CPSF(GZB20230931)the support from Initial Energy Science&Technology Co.,Ltd(IEST)。
文摘The dissolution of iron from the cathode and electrode/electrolyte interface(EEI)during long cycles significantly accelerates the aging process of LiFePO_(4)(LFP)/graphite batteries;there is a lack of systematic understanding of the spatial distribution of the EEI interface layer and the dissolve of Fe ions,especially in terms of the mechanism of the cathode-electrolyte interphase(CEI),solid electrolyte interphase(SEI),and iron dissolution.In this study,aged cells were subjected to continuous activation with constant current and multi-step segmented indirect activation(IA)and analyzed for capacity fade,impedance growth,and active Li^(+)mass loss at the EEI and nanoscale levels.The interaction between dissolved Fe^(2+)and the EEI in LFP/graphite pouch batteries was proposed and verified.The findings indicate that during IA process,the electric field facilitates the migration of solvated ions toward the electrodes,while simultaneously inhibiting the formation of organic species such as ROCO_(2)Li.The SEI primarily consists of a mixture of organic and inorganic small molecules,forming a continuous and uniform film on the electrode surface.This study demonstrates that IA favors the formation of a uniform EEI and offers constructive insights for advancing accelerated lifetime prediction strategies in lithium-ion batteries.
基金supported by the NIH RF1 grant NS119477 jointly funded by NINDS and NIA(to RM).
文摘Cells of the central nervous system(CNS)are privileged in lying behind the blood-brain barrier(BBB).Unlike blood vessels in other organs,CNS blood vessels are unique in displaying high electrical resistance and low permeability.With this unique structure and function,the BBB prevents potentially harmful blood components such as serum proteins,inflammatory cytokines,and inflammatory leukocytes from entering the hallowed space of the CNS and wreaking havoc.In addition to these“tightness”properties,the BBB has an array of specialized transporters designed to import essential nutrients.
基金supported by the National Natural Science Foundation of China (Grant Nos.T2325004 and 52161160330)the National Natural Science Foundation of China (Grants No.12504233)+2 种基金Advanced MaterialsNational Science and Technology Major Project (Grant No.2024ZD0606900)the Talent Hub for “AI+New Materials” Basic Researchthe Key Research and Development Program of Ningbo (Grant No.2025Z088)。
文摘The functional properties of glasses are governed by their formation history and the complex relaxation processes they undergo.However,under extreme conditions,glass behaviors are still elusive.In this study,we employ simulations with varied protocols to evaluate the effectiveness of different descriptors in predicting mechanical properties across both low-and high-pressure regimes.Our findings demonstrate that conventional structural and configurational descriptors fail to correlate with the mechanical response following pressure release,whereas the activation energy descriptor exhibits robust linearity with shear modulus after correcting for pressure effects.Notably,the soft mode parameter emerges as an ideal and computationally efficient alternative for capturing this mechanical behavior.These findings provide critical insights into the influence of pressure on glassy properties,integrating the distinct features of compressed glasses into a unified theoretical framework.
基金the National Natural Science Foundation of China(No.21961015)the Natural Science Foundation of Jiangxi Province(No.20202ACBL203005)for their financial support.
文摘Disclosed herein is a novel Rh/Ag co-catalyzed S=NH directed C–H activation and C–H/N–H bond functionalization protocol of free NH-sulfoximines with hypervalent iodonium ylides.With the aid of AgOTf,these C–H functionalization/cyclization sequences could be achieved at room temperature conditions.The reaction employed EtOH as a“green”solvent and low catalyst loading was required under an oxygen/water-insensitive condition.Under this mild protocol,a wide range of polyheterocyclic sulfoximines bearing fused saturated carbo(hetero)cycles are readily prepared,even toward a complex pharmaceutical Folliculin analog.
基金supported by National Natural Science Foundation of China(No.81973166)Science and Technology Commission of Shanghai Municipality(No.22XD1424600)+4 种基金Natural Science Foundation of Shanghai Municipality(No.22ZR1474100)Taishan Scholar Foundation of Shandong Province(No.tsqn202306322)National Key R&D Program of China(No.2021YFC2300700)Shandong Laboratory Program(No.SYS202205)Shandong Provincial Natural Science Foundation(Nos.ZR2023LSW003 and ZR2023JQ028)。
文摘The development of enantioselective C-H macrocyclizations to efficiently access structurally diversified macrocycles is highly desirable,but remain a big challenge.Herein,we reported the first rhodium(Ⅲ)-catalyzed asymmetric intramolecular C-H macrocyclization,enabling the efficient synthesis of structurally diverse enantioenriched macrocycles.This robust enantioselective C-H macrocyclization has a broad functional group tolerance,excellent enantioselectivities(up to 98.5:1.5 e.r.)and a mild reaction condition,releasing CO_(2)as the single by-product.More significantly,the resulting unique enantioenriched19-membered macrocycle 2f was found to demonstrate a potent in vitro anti-Zika virus(ZIKV)activity without obvious cytotoxicity.Further investigation revealed that the anti-ZIKV activity is presumably attributed to an autophagy inhibition in the early stage of viral infection by down-regulating the expression of autophagy related gene Atg12.
