The development of sustainable and efficient catalytic systems for the formation C-C,C-N,C-o bonds is a fundamental goal in modern synthetic chemistry.We present a biomass-derived Cu/Chitosan-800 catalyst that facilit...The development of sustainable and efficient catalytic systems for the formation C-C,C-N,C-o bonds is a fundamental goal in modern synthetic chemistry.We present a biomass-derived Cu/Chitosan-800 catalyst that facilitates a range of carbenoid insertion reactions into C-H,N-H,and O-H bonds.This catalyst demonstrates remarkable activity,enabling the functionalization of diverse substrates,including the late-stage modification of drug molecules with up to 95%yield and good recyclability.Our findings highlight the catalyst's potential in advancing environmentally friendly chemical transformations,offering a promising tool for pharmaceutical synthesis and organic synthesis.展开更多
Late-stage functionalization is an attractive strategy that allows chemists to bypass lengthy synthetic processes,facilitating the rapid generation of drug analogs with potentially enhanced pharmacokinetic and pharmac...Late-stage functionalization is an attractive strategy that allows chemists to bypass lengthy synthetic processes,facilitating the rapid generation of drug analogs with potentially enhanced pharmacokinetic and pharmacological properties.This study describes a novel approach for cross-dehydrogenative oxyalkylation,leveraging a unique g-ray-enabled photoredox process to generate oxyalkyl radicals,followed by a Minisci-type addition in an aqueous solution.The metal-and oxidant-free aqueous conditions,coupled with excellent functional group compatibility,establish this method as a versatile protocol for the late-stage oxyalkylation of unprotected,structurally complex drug molecules.Notably,this method demonstrated improved pharmacokinetics in hydroxymethylated fibroblast activation protein inhibitor(FAPI)molecules,highlighting its potential to accelerate drug discovery efforts.展开更多
Given the broad applicability of carbazole structural moieties in materials science and medicinal chemistry,significant efforts have been devoted to developing efficient synthetic catalytic methodologies to access thi...Given the broad applicability of carbazole structural moieties in materials science and medicinal chemistry,significant efforts have been devoted to developing efficient synthetic catalytic methodologies to access this valuable scaffold.Catalyzed direct Csp^(2)-H functionalization provides an effective and costefficient approach to synthesizing carbazoles from simple and readily available starting materials,ensuring a promising path characterized by excellent atom and step economy.This review highlights the substantial progress made in the last 10 years in advancing catalytic Csp^(2)-H functionalization techniques for synthesizing carbazoles.展开更多
Carbon-based air cathodes offer low cost,high electrical conductivity,and structural tunability.However,they suffer from limited catalytic activity and inefficient gas transport,and they typically rely on noble metal ...Carbon-based air cathodes offer low cost,high electrical conductivity,and structural tunability.However,they suffer from limited catalytic activity and inefficient gas transport,and they typically rely on noble metal additives or complex multilayer configurations.To tackle these issues,this study devised a self-activated integrated carbon-based air cathode.By integrating in situ catalytic site construction with structural optimization,the strategy not only induces the formation of oxygen functional groups(─C─OH,─C═O,─COOH),hierarchical pores,and uniformly distributed active sites,but also establishes a favorable electronic and mass-transport environment.Furthermore,the roll-pressing-based integrated design streamlines electrode construction,reinforces interfacial bonding,and significantly enhances mechanical stability.Density functional theory(DFT)calculations show that oxygen functional groups initiate hydrogen bonding interaction and promote charge enrichment,which improves the activity of the cathode and facilitates intermediate adsorption/desorption in oxygen reduction and evolution reactions processes.As a result,the integrated air cathode-based rechargeable zinc-air batteries(RZABs)achieve a high specific capacity of 811 mAh g^(-1).It also performs well in quasi-solid-state RZABs and silicon-air batteries systems across a wide temperature range,demonstrating strong adaptability and application potential.This study provides a scalable and cost-effective design strategy for high-performance carbon-based air cathodes,offering new insights into advancing durable and practical metal-air energy systems.展开更多
Late-stage modification of peptides and proteins meets the increasing demand in biochemical and pharmaceutical communities. These modification strategies could provide functionalized nonproteinogenic analogues with en...Late-stage modification of peptides and proteins meets the increasing demand in biochemical and pharmaceutical communities. These modification strategies could provide functionalized nonproteinogenic analogues with enhanced biological activities or improved therapeutic capabilities compared to their natural counterparts. Recent years, transition-metal-promoted functionalization of ubiquitous C-H bonds has been emerged as a powerful and tunable tool in this area, both for backbone diversifications and labeling of specific moieties. These reactions were flexible and expedient in both academic and industrial laboratories, especially considering their atom and step-economy, good functional group compatibility, accurate site selectivity. This review surveys the progress achieved in the late-stage modification of peptides and proteins utilizing transition-metal-catalyzed C-H functionalization with C-C and C-X(F, Cl, O, N, B, etc.) bonds formation.展开更多
2,3-Dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) is a stoichiometric oxidant that is frequently used in traditional organic synthesis. Recently, the rapid development of organic electrochemistry has led to new advancem...2,3-Dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) is a stoichiometric oxidant that is frequently used in traditional organic synthesis. Recently, the rapid development of organic electrochemistry has led to new advancements in DDQ-catalyzed C—H bonds functionalization. Moreover, the challenging C—H functionalization of electron-deficient arenes has been achieved through the merger of electrochemical DDQ catalysis and photoirradiation. In addition, the synthetic utility of electrophotochemical DDQ catalysis was further demonstrated by the nucleophilic aromatic substitution (SNAr) reaction of unactivated aryl fluorides. The recent developments in electro- and electrophotochemical DDQ-catalyzed C—H/C—F func- tionalizations with attention to their strategies and mechanistic insights are summarized. It is hoped that this not only deepens the understanding of this field, but also helps relevant researchers expand the application scope of DDQ catalysis.展开更多
As naturally abundant and readily available starting materials,alcohols are frequently employed as synthetic building blocks in organic synthesis.The hydroxyl group,which serves as the characteristic functional group ...As naturally abundant and readily available starting materials,alcohols are frequently employed as synthetic building blocks in organic synthesis.The hydroxyl group,which serves as the characteristic functional group of alcohols,is the primary reactive site for these compounds.Consequently,dehydroxylative functionalization reaction is one of the representative transformations of alcohols and has demonstrated significant potential in constructing new chemical bonds.Over the past decade,this research field has received continuous and extensive attention.This review comprehensively summarizes the recent advances in the dehydroxylative functionalization of alcohols,discussing on the reaction methodologies and mechanisms for constructing carbon-heteroatom and carbon-carbon bonds from alcohols.展开更多
Difunctionalization of unsaturated hydrocarbons is a pivotal synthetic strategy enabling the conversion of alkenes and alkynes into high value-added compounds.It allows for the introduction of two functional groups in...Difunctionalization of unsaturated hydrocarbons is a pivotal synthetic strategy enabling the conversion of alkenes and alkynes into high value-added compounds.It allows for the introduction of two functional groups into the unsaturated bond in a single step,facilitating the efficient construction of complex molecular architectures,which has been widely utilized in material chemistry,pharmaceutical and fine chemical synthesis.Recently,significant progress has been made via free radical-mediated difunctionalization due to the extensive application of photocatalysis.However,highly selective difunc-tionalization reactions still remain challenging.The research progress of selective difunctionalization of unsaturated hydro-carbons using a free radical addition/functional group migration strategy over the past decade is summarized,and synthetic strategies and key reaction steps are systematically elaborated.展开更多
Visible-light-mediated O-H functionalization reactions of alcohols with diazo compounds have been fully developed in recent years.However,alkenyl and acetylenic alcohols were rarely examined in these reactions due to ...Visible-light-mediated O-H functionalization reactions of alcohols with diazo compounds have been fully developed in recent years.However,alkenyl and acetylenic alcohols were rarely examined in these reactions due to the inevitable side reactions involving cycloaddition.Herein,the visible-light-mediated O-H functionalization reactions of alkenyl alcohols with diazo compounds were developed.This process competed favorably with the cycloaddition reaction.A series of multifunctional ethers were provided in low to high yields with aryldiazoacetates or 3-diazooxindoles.Biologically relevant spirooxindole-fused oxacycle could be easily accessed from the O-H functionalization product of alkenyl alcohol and 3-diazooxindole.展开更多
Asymmetric allylic C—H functionalization is a valuable and challenging research area. Different from the conventional direct allylic C—H cleavage strategy, transition metal-catalyzed migratory allylic substitution o...Asymmetric allylic C—H functionalization is a valuable and challenging research area. Different from the conventional direct allylic C—H cleavage strategy, transition metal-catalyzed migratory allylic substitution of remote dienes has emerged as a new route to achieve allylic C—H functionalization enantioselectively. This review provides a detailed summary of the development and advance of this strategy, introduces the related mechanistic processes, and discusses the area based on the types of catalysts and products.展开更多
This study investigates the properties of high-purity starches extracted from Polygonum multiflorum(PMS)and Smilax glabra(SGS).The starches were characterized by scanning electron microscopy,Fouriertransform infrared ...This study investigates the properties of high-purity starches extracted from Polygonum multiflorum(PMS)and Smilax glabra(SGS).The starches were characterized by scanning electron microscopy,Fouriertransform infrared spectroscopy,X-ray diffraction,high-performance anion-exchange chromatography,and differential scanning calorimetry.Significant differences were observed in their morphological,physicochemical,and functional properties.PMS had a smaller particle size(13.68 μm),irregular polygonal shape,A-type,lower water absorption(62.67 %),and higher oil absorption(51.17 %).In contrast,SGS exhibited larger particles(31.75 μm),a nearly spherical shape,B-type,higher crystallinity(50.66 %),and greater amylose content(21.54 %),with superior thermal stability,shear resistance,and gelatinization enthalpy.SGS also contained higher resistant starch(83.28 %) and longer average chain length(20.58 %),but showed lower solubility,swelling power,light transmittance,and freeze-thaw stability.The physicochemical properties differences in crystal pattern and particle morphology between PMS and SGS lead to distinct behaviors during in vitro digestion and fermentation.These findings highlight the potential of medicinal plant starches in functional ingredients and industrial processes.展开更多
Gauss radial basis functions(GRBF)are frequently employed in data fitting and machine learning.Their linear independence property can theoretically guarantee the avoidance of data redundancy.In this paper,one of the m...Gauss radial basis functions(GRBF)are frequently employed in data fitting and machine learning.Their linear independence property can theoretically guarantee the avoidance of data redundancy.In this paper,one of the main contributions is proving this property using linear algebra instead of profound knowledge.This makes it easy to read and understand this fundamental fact.The proof of linear independence of a set of Gauss functions relies on the constructing method for one-dimensional space and on the deducing method for higher dimensions.Additionally,under the condition of preserving the same moments between the original function and interpolating function,both the interpolating existence and uniqueness are proven for GRBF in one-dimensional space.The final work demonstrates the application of the GRBF method to locate lunar olivine.By combining preprocessed data using GRBF with the removing envelope curve method,a program is created to find the position of lunar olivine based on spectrum data,and the numerical experiment shows that it is an effective scheme.展开更多
The preparation of specifically iodine-125 (125I)-labeled peptides of high purity and specific activity represents a key tool for the detailed characterization of their binding properties in interaction with their bin...The preparation of specifically iodine-125 (125I)-labeled peptides of high purity and specific activity represents a key tool for the detailed characterization of their binding properties in interaction with their binding partners. Early synthetic methods for the incorporation of iodine faced challenges such as harsh reaction conditions, the use of strong oxidants and low reproducibility. Herein, we review well-established radiolabeling strategies available to incorporate radionuclide into a protein of interest, and our long-term experience with a mild, simple and generally applicable technique of 125I late-stage-labeling of biomolecules using the Pierce iodination reagent for the direct solid-phase oxidation of radioactive iodide. General recommendations, tips, and details of optimized chromatographic conditions to isolate pure, specifically 125I-mono-labeled biomolecules are illustrated on a diverse series of (poly)peptides, ranging up to 7.6 kDa and 67 amino acids (aa). These series include peptides that contain at least one tyrosine or histidine residue, along with those featuring disulfide crosslinking or lipophilic derivatization. This mild and straightforward late-stage-labeling technique is easily applicable to longer and more sensitive proteins, as demonstrated in the cases of the insulin-like growth factor binding protein-3 (IGF-BP-3) (29 kDa and 264 aa) and the acid-labile subunit (ALS) (93 kDa and 578 aa).展开更多
Chemical recycling/upcycling of plastics has emerged as one of the most promising strategies for the plastic circular economy,enabling the depolymerization and functionalization of plastics into valuable monomers and ...Chemical recycling/upcycling of plastics has emerged as one of the most promising strategies for the plastic circular economy,enabling the depolymerization and functionalization of plastics into valuable monomers and chemicals.However,studies on the depolymerization and functionalization of challenging super engineering plastics have remained in early stage and underexplored.In this review,we would like to discuss the representative accomplishments and mechanism insights on chemical protocols achieved in depolymerization of super engineering plastics,especially for poly(phenylene sulfide)(PPS),poly(aryl ether)s including poly(ether ether ketone)(PEEK),polysulfone(PSU),polyphenylsulfone(PPSU)and polyethersulfone(PES).We anticipate that this review will provide an overall perspective on the current status and future trends of this emerging field.展开更多
The transition metal-catalyzed C–H activation have been considered as increasingly useful approach for installing new functional groups onto organic small molecules due to their high step-and atom-economy,the abundan...The transition metal-catalyzed C–H activation have been considered as increasingly useful approach for installing new functional groups onto organic small molecules due to their high step-and atom-economy,the abundance of hydrocarbon compounds,and the potential for late-stage functionalization of complex organic molecules.The ortho-and meta-C-H activation and functionalization of aromatic compounds have been widely explored in recent years,however the distal para-C-H activation and functionalization has remained a significant challenge because of the difficulty in forming energetically favorable metallacyclic transition states.The utilization of appropriate directing groups or templates as well as the meticulous design of catalysts and ligands has proven to be effective in transition-metal-catalyzed remote para-C-H bonds activation and functionalization of aromatic compounds.This review aims to summarize the strategies for controlling para-selective C–H functionalization using the directing group,template engineering,and catalyst/ligand design under transition metals catalysis in recent years.展开更多
Cp_(2)TiCl_(2) as a Lewis acid precursor and nicotinic acid as a ligand have been used synergistically for the one-pot synthesis of 2-(N-substituted amino)-1,4-naphthoquinones.This method establishes a general strateg...Cp_(2)TiCl_(2) as a Lewis acid precursor and nicotinic acid as a ligand have been used synergistically for the one-pot synthesis of 2-(N-substituted amino)-1,4-naphthoquinones.This method establishes a general strategy for the functionalization and conversion of C-H bonds of 1,4-naphthoquinones into C-N bonds,providing an effective route to synthesize 2-(N-substituted amino)-1,4-naphthoquinone with high yield under mild conditions.Additionally,the synergistic catalytic mechanism was investigated by 1H NMR titration experiments and LC-MS analysis,with experimental results sufficiently and consistently supporting the proposed mechanism of the catalytic cycle.展开更多
Increased human and industrial activities have exacerbated the release of toxic materials and acute envi-ronmental pollution in recent times.Biochar,a carbon-rich material produced from biomass,is gaining momentum as ...Increased human and industrial activities have exacerbated the release of toxic materials and acute envi-ronmental pollution in recent times.Biochar,a carbon-rich material produced from biomass,is gaining momentum as a versatile material for attaining a sustainable environment.The study reviews the application of functionalized biochar for energy storage,environmental remediation,catalysis,and sustainable agriculture,aiming to achieve a greener future.Thedeployment of crop residues as a renewable feedstock for biochar,and their properties,compositions,modification,and functionalization techniques are also discussed.Additionally,the avenues for applying functionalized biochar to achieve a greener future,future trends and innovations,challenges,and future research directions are highlighted.Despite the limitations of scalability,ecotoxicological risks,logistical issues,lack of characterization protocols,high production costs,poor social acceptance,and inadequate policy and regulatory frameworks,functionalized biochar offers a better surface area,improved porosity,enhanced functional groups,and higher recoverability,leading to improved performance,adsorption capacity,biodegradability,and applications in specialized fields.Future research should prioritize standardization,scalability,cost reduction strategies,expansion of application areas,integration of emerging tools such as artificial intelligence and predictive modeling,and the development of policy and regulatory frameworks,ensuring that biochar’s full potential is harnessed effectively to support a low-carbon,resource-efficient future and global sustainability goals.展开更多
In contrast to the predominant mono or difunctionalization of alkenes,the multi-site functionalization of alkenes involving the synergistic formation of more than two new C–C or C–X bonds is much challenging,especia...In contrast to the predominant mono or difunctionalization of alkenes,the multi-site functionalization of alkenes involving the synergistic formation of more than two new C–C or C–X bonds is much challenging,especially for developing new reaction pathway to afford the functional heterocycle compounds with aggregation-induced emission(AIE)property has been rarely reported.In present work,the multi-site functionalization of in situ generated alkenes with indoles has been developed for the synthesis of diversely functionalized carbazoles through the synergistic construction of multiple C–C bonds and C=O bond.A proposed reaction sequence involving C–H alkenylation/radical oxygen atom transfer/Diels-Alder cycloaddition/dehydrogenative aromatization was supported by experiments and density functional theory calculations.Further derivative carbazole-linked-quinoxaline skeletons represent a class of AIEgens with acceptor-donor-acceptor configuration,which generated the desired twisted intramolecular charge transfer(TICT)AIE properties and could be used as fluorescent probes for detecting the micrometer-sized phase separation of polymer blends.The protocol provides a concise route for the synthesis and application of carbazole-based AIE luminogens.展开更多
Purpose: This study focused on maintaining and improving the walking function of late-stage older individuals while longitudinally tracking the effects of regular exercise programs in a day-care service specialized fo...Purpose: This study focused on maintaining and improving the walking function of late-stage older individuals while longitudinally tracking the effects of regular exercise programs in a day-care service specialized for preventive care over 5 years, using detailed gait function measurements with an accelerometer-based system. Methods: Seventy individuals (17 male and 53 female) of a daycare service in Tokyo participated in a weekly exercise program, meeting 1 - 2 times. The average age of the participants at the start of the program was 81.4 years. Gait function, including gait speed, stride length, root mean square (RMS) of acceleration, gait cycle time and its standard deviation, and left-right difference in stance time, was evaluated every 6 months. Results: Gait speed and stride length improved considerably within six months of starting the exercise program, confirming an initial improvement in gait function. This suggests that regular exercise programs can maintain or improve gait function even age groups that predictably have a gradual decline in gait ability due to enhanced age. In the long term, many indicators tended to approach baseline values. However, the exercise program seemingly counteracts age-related changes in gait function and maintains a certain level of function. Conclusions: While a decline in gait ability with aging is inevitable, establishing appropriate exercise habits in late-stage older individuals may contribute to long-term maintenance of gait function.展开更多
Spinal cord injury represents a severe form of central nervous system trauma for which effective treatments remain limited.Microglia is the resident immune cells of the central nervous system,play a critical role in s...Spinal cord injury represents a severe form of central nervous system trauma for which effective treatments remain limited.Microglia is the resident immune cells of the central nervous system,play a critical role in spinal cord injury.Previous studies have shown that microglia can promote neuronal survival by phagocytosing dead cells and debris and by releasing neuroprotective and anti-inflammatory factors.However,excessive activation of microglia can lead to persistent inflammation and contribute to the formation of glial scars,which hinder axonal regeneration.Despite this,the precise role and mechanisms of microglia during the acute phase of spinal cord injury remain controversial and poorly understood.To elucidate the role of microglia in spinal cord injury,we employed the colony-stimulating factor 1 receptor inhibitor PLX5622 to deplete microglia.We observed that sustained depletion of microglia resulted in an expansion of the lesion area,downregulation of brain-derived neurotrophic factor,and impaired functional recovery after spinal cord injury.Next,we generated a transgenic mouse line with conditional overexpression of brain-derived neurotrophic factor specifically in microglia.We found that brain-derived neurotrophic factor overexpression in microglia increased angiogenesis and blood flow following spinal cord injury and facilitated the recovery of hindlimb motor function.Additionally,brain-derived neurotrophic factor overexpression in microglia reduced inflammation and neuronal apoptosis during the acute phase of spinal cord injury.Furthermore,through using specific transgenic mouse lines,TMEM119,and the colony-stimulating factor 1 receptor inhibitor PLX73086,we demonstrated that the neuroprotective effects were predominantly due to brain-derived neurotrophic factor overexpression in microglia rather than macrophages.In conclusion,our findings suggest the critical role of microglia in the formation of protective glial scars.Depleting microglia is detrimental to recovery of spinal cord injury,whereas targeting brain-derived neurotrophic factor overexpression in microglia represents a promising and novel therapeutic strategy to enhance motor function recovery in patients with spinal cord injury.展开更多
基金supported by the National Natural Science Foundation of China(22371083,22001086)the Fundamental Research Funds for the Central Universities(2024BRB003,HUST 2020kfyXJJS094)+1 种基金the State Key Laboratory of Natural and Biomimetic Drugs,Peking University(K202409)the Innovation and Talent Recruitment Base of New Energy Chemistry and Device(B21003).
文摘The development of sustainable and efficient catalytic systems for the formation C-C,C-N,C-o bonds is a fundamental goal in modern synthetic chemistry.We present a biomass-derived Cu/Chitosan-800 catalyst that facilitates a range of carbenoid insertion reactions into C-H,N-H,and O-H bonds.This catalyst demonstrates remarkable activity,enabling the functionalization of diverse substrates,including the late-stage modification of drug molecules with up to 95%yield and good recyclability.Our findings highlight the catalyst's potential in advancing environmentally friendly chemical transformations,offering a promising tool for pharmaceutical synthesis and organic synthesis.
基金funded by the Ministry of Science and Technology of the People’s Republic of China(2021YFA1601400)the National Natural Science Foundation of China(22225603 and 22441051)the New Cornerstone Science Foundation(The XPLORER PRIZE)and Changping Laboratory to Z.L.,and the National Nature Science Foundation of China(22306005)to B.-S.M.
文摘Late-stage functionalization is an attractive strategy that allows chemists to bypass lengthy synthetic processes,facilitating the rapid generation of drug analogs with potentially enhanced pharmacokinetic and pharmacological properties.This study describes a novel approach for cross-dehydrogenative oxyalkylation,leveraging a unique g-ray-enabled photoredox process to generate oxyalkyl radicals,followed by a Minisci-type addition in an aqueous solution.The metal-and oxidant-free aqueous conditions,coupled with excellent functional group compatibility,establish this method as a versatile protocol for the late-stage oxyalkylation of unprotected,structurally complex drug molecules.Notably,this method demonstrated improved pharmacokinetics in hydroxymethylated fibroblast activation protein inhibitor(FAPI)molecules,highlighting its potential to accelerate drug discovery efforts.
基金support and funding by the European Union-Next Generation EU under the Italian Ministry of University and Research (MUR) National Innovation Ecosystem (No.ECS00000041-VITALITY and also “Ecosistema TECH4YOU-(Spoke 3-Goal 3.5)MUR is thanked for PRIN-PNRR 2022 project "P2022XKWH7-Circular Waste+3 种基金The University of Perugia is acknowledged for financial support to the university project “Fondo Ricerca di Ateneo,edizione 2022”The National Ph D program in Catalysis coordinated by the University of Perugia is also thankedthe financial supports of key research and development and technology transfer projects of Inner Mongolia Autonomous Region (No.2025KJHZ0008)major special projects of science and technology of Ordos (No.2022EEDSKJZDZX003)。
文摘Given the broad applicability of carbazole structural moieties in materials science and medicinal chemistry,significant efforts have been devoted to developing efficient synthetic catalytic methodologies to access this valuable scaffold.Catalyzed direct Csp^(2)-H functionalization provides an effective and costefficient approach to synthesizing carbazoles from simple and readily available starting materials,ensuring a promising path characterized by excellent atom and step economy.This review highlights the substantial progress made in the last 10 years in advancing catalytic Csp^(2)-H functionalization techniques for synthesizing carbazoles.
基金funded by the National Nature Science Foundation of China(62264006,62574102)“Thousand Talents Program”of Yunnan Province for Young Talents,Innovative Research Teams(in Science and Technology)in the University of Yunnan Province(IRTSTYN),XingDian Talent Support Program for Young Talents,and Frontier Research Team of Kunming University 2023,The Basic Research Project of Yunnan Province(Nos.202201AU070022)+2 种基金Kunming University Talent Introduction Fund(Nos.YJL20024)Yunnan Province Education Department Scientific Research Fund Project(Nos.2024Y759)Undergraduate Innovation and Entrepreneurship Training Program Project of Yunnan Provincial(202411393005)。
文摘Carbon-based air cathodes offer low cost,high electrical conductivity,and structural tunability.However,they suffer from limited catalytic activity and inefficient gas transport,and they typically rely on noble metal additives or complex multilayer configurations.To tackle these issues,this study devised a self-activated integrated carbon-based air cathode.By integrating in situ catalytic site construction with structural optimization,the strategy not only induces the formation of oxygen functional groups(─C─OH,─C═O,─COOH),hierarchical pores,and uniformly distributed active sites,but also establishes a favorable electronic and mass-transport environment.Furthermore,the roll-pressing-based integrated design streamlines electrode construction,reinforces interfacial bonding,and significantly enhances mechanical stability.Density functional theory(DFT)calculations show that oxygen functional groups initiate hydrogen bonding interaction and promote charge enrichment,which improves the activity of the cathode and facilitates intermediate adsorption/desorption in oxygen reduction and evolution reactions processes.As a result,the integrated air cathode-based rechargeable zinc-air batteries(RZABs)achieve a high specific capacity of 811 mAh g^(-1).It also performs well in quasi-solid-state RZABs and silicon-air batteries systems across a wide temperature range,demonstrating strong adaptability and application potential.This study provides a scalable and cost-effective design strategy for high-performance carbon-based air cathodes,offering new insights into advancing durable and practical metal-air energy systems.
基金the support from the National Key R&D Program of China(No. 2017YFA0505400)the National Natural Science Foundation of China (Nos. 21572214, 21702200)
文摘Late-stage modification of peptides and proteins meets the increasing demand in biochemical and pharmaceutical communities. These modification strategies could provide functionalized nonproteinogenic analogues with enhanced biological activities or improved therapeutic capabilities compared to their natural counterparts. Recent years, transition-metal-promoted functionalization of ubiquitous C-H bonds has been emerged as a powerful and tunable tool in this area, both for backbone diversifications and labeling of specific moieties. These reactions were flexible and expedient in both academic and industrial laboratories, especially considering their atom and step-economy, good functional group compatibility, accurate site selectivity. This review surveys the progress achieved in the late-stage modification of peptides and proteins utilizing transition-metal-catalyzed C-H functionalization with C-C and C-X(F, Cl, O, N, B, etc.) bonds formation.
文摘2,3-Dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) is a stoichiometric oxidant that is frequently used in traditional organic synthesis. Recently, the rapid development of organic electrochemistry has led to new advancements in DDQ-catalyzed C—H bonds functionalization. Moreover, the challenging C—H functionalization of electron-deficient arenes has been achieved through the merger of electrochemical DDQ catalysis and photoirradiation. In addition, the synthetic utility of electrophotochemical DDQ catalysis was further demonstrated by the nucleophilic aromatic substitution (SNAr) reaction of unactivated aryl fluorides. The recent developments in electro- and electrophotochemical DDQ-catalyzed C—H/C—F func- tionalizations with attention to their strategies and mechanistic insights are summarized. It is hoped that this not only deepens the understanding of this field, but also helps relevant researchers expand the application scope of DDQ catalysis.
基金Project supported by the Technology Program of Zhoukou(No.2023GG02054)the Natural Science Foundation of Shandong Province(No.ZR2024MB082)the Open Foundation Supported by Jiangsu Province Engineering Research Center of Precision Diagnostics and Therapeutics Development(No.SDGC2401)。
文摘As naturally abundant and readily available starting materials,alcohols are frequently employed as synthetic building blocks in organic synthesis.The hydroxyl group,which serves as the characteristic functional group of alcohols,is the primary reactive site for these compounds.Consequently,dehydroxylative functionalization reaction is one of the representative transformations of alcohols and has demonstrated significant potential in constructing new chemical bonds.Over the past decade,this research field has received continuous and extensive attention.This review comprehensively summarizes the recent advances in the dehydroxylative functionalization of alcohols,discussing on the reaction methodologies and mechanisms for constructing carbon-heteroatom and carbon-carbon bonds from alcohols.
文摘Difunctionalization of unsaturated hydrocarbons is a pivotal synthetic strategy enabling the conversion of alkenes and alkynes into high value-added compounds.It allows for the introduction of two functional groups into the unsaturated bond in a single step,facilitating the efficient construction of complex molecular architectures,which has been widely utilized in material chemistry,pharmaceutical and fine chemical synthesis.Recently,significant progress has been made via free radical-mediated difunctionalization due to the extensive application of photocatalysis.However,highly selective difunc-tionalization reactions still remain challenging.The research progress of selective difunctionalization of unsaturated hydro-carbons using a free radical addition/functional group migration strategy over the past decade is summarized,and synthetic strategies and key reaction steps are systematically elaborated.
文摘Visible-light-mediated O-H functionalization reactions of alcohols with diazo compounds have been fully developed in recent years.However,alkenyl and acetylenic alcohols were rarely examined in these reactions due to the inevitable side reactions involving cycloaddition.Herein,the visible-light-mediated O-H functionalization reactions of alkenyl alcohols with diazo compounds were developed.This process competed favorably with the cycloaddition reaction.A series of multifunctional ethers were provided in low to high yields with aryldiazoacetates or 3-diazooxindoles.Biologically relevant spirooxindole-fused oxacycle could be easily accessed from the O-H functionalization product of alkenyl alcohol and 3-diazooxindole.
文摘Asymmetric allylic C—H functionalization is a valuable and challenging research area. Different from the conventional direct allylic C—H cleavage strategy, transition metal-catalyzed migratory allylic substitution of remote dienes has emerged as a new route to achieve allylic C—H functionalization enantioselectively. This review provides a detailed summary of the development and advance of this strategy, introduces the related mechanistic processes, and discusses the area based on the types of catalysts and products.
基金supported by the National Natural Science Foundation of China (No.82174074)。
文摘This study investigates the properties of high-purity starches extracted from Polygonum multiflorum(PMS)and Smilax glabra(SGS).The starches were characterized by scanning electron microscopy,Fouriertransform infrared spectroscopy,X-ray diffraction,high-performance anion-exchange chromatography,and differential scanning calorimetry.Significant differences were observed in their morphological,physicochemical,and functional properties.PMS had a smaller particle size(13.68 μm),irregular polygonal shape,A-type,lower water absorption(62.67 %),and higher oil absorption(51.17 %).In contrast,SGS exhibited larger particles(31.75 μm),a nearly spherical shape,B-type,higher crystallinity(50.66 %),and greater amylose content(21.54 %),with superior thermal stability,shear resistance,and gelatinization enthalpy.SGS also contained higher resistant starch(83.28 %) and longer average chain length(20.58 %),but showed lower solubility,swelling power,light transmittance,and freeze-thaw stability.The physicochemical properties differences in crystal pattern and particle morphology between PMS and SGS lead to distinct behaviors during in vitro digestion and fermentation.These findings highlight the potential of medicinal plant starches in functional ingredients and industrial processes.
基金Supported by the National Basic Research Program of China(2012CB025904)Zhengzhou Shengda University of Economics,Business and Management(SD-YB2025085)。
文摘Gauss radial basis functions(GRBF)are frequently employed in data fitting and machine learning.Their linear independence property can theoretically guarantee the avoidance of data redundancy.In this paper,one of the main contributions is proving this property using linear algebra instead of profound knowledge.This makes it easy to read and understand this fundamental fact.The proof of linear independence of a set of Gauss functions relies on the constructing method for one-dimensional space and on the deducing method for higher dimensions.Additionally,under the condition of preserving the same moments between the original function and interpolating function,both the interpolating existence and uniqueness are proven for GRBF in one-dimensional space.The final work demonstrates the application of the GRBF method to locate lunar olivine.By combining preprocessed data using GRBF with the removing envelope curve method,a program is created to find the position of lunar olivine based on spectrum data,and the numerical experiment shows that it is an effective scheme.
基金Institutional support was provided by the project of the Czech Academy of Sciences,Czech Republic(to the Institute of Organic Chemistry and Biochemistry)(Project No.:RVO 61388963)This work was supported by the project National Institute for Research of Metabolic and Cardiovascular Diseases(Programme EXCELES)funded by the European Union's Next Generation EU(Project No.:LX22NPO5104)the Czech Science Foundation,Czech Republic(Grant No.:23-05805S).
文摘The preparation of specifically iodine-125 (125I)-labeled peptides of high purity and specific activity represents a key tool for the detailed characterization of their binding properties in interaction with their binding partners. Early synthetic methods for the incorporation of iodine faced challenges such as harsh reaction conditions, the use of strong oxidants and low reproducibility. Herein, we review well-established radiolabeling strategies available to incorporate radionuclide into a protein of interest, and our long-term experience with a mild, simple and generally applicable technique of 125I late-stage-labeling of biomolecules using the Pierce iodination reagent for the direct solid-phase oxidation of radioactive iodide. General recommendations, tips, and details of optimized chromatographic conditions to isolate pure, specifically 125I-mono-labeled biomolecules are illustrated on a diverse series of (poly)peptides, ranging up to 7.6 kDa and 67 amino acids (aa). These series include peptides that contain at least one tyrosine or histidine residue, along with those featuring disulfide crosslinking or lipophilic derivatization. This mild and straightforward late-stage-labeling technique is easily applicable to longer and more sensitive proteins, as demonstrated in the cases of the insulin-like growth factor binding protein-3 (IGF-BP-3) (29 kDa and 264 aa) and the acid-labile subunit (ALS) (93 kDa and 578 aa).
基金supported by the National Natural Science Foundation of China(Nos.22125103 and 22301077)STCSM(22JC140100)Shanghai Pujiang Program(No.22PJ1403200)。
文摘Chemical recycling/upcycling of plastics has emerged as one of the most promising strategies for the plastic circular economy,enabling the depolymerization and functionalization of plastics into valuable monomers and chemicals.However,studies on the depolymerization and functionalization of challenging super engineering plastics have remained in early stage and underexplored.In this review,we would like to discuss the representative accomplishments and mechanism insights on chemical protocols achieved in depolymerization of super engineering plastics,especially for poly(phenylene sulfide)(PPS),poly(aryl ether)s including poly(ether ether ketone)(PEEK),polysulfone(PSU),polyphenylsulfone(PPSU)and polyethersulfone(PES).We anticipate that this review will provide an overall perspective on the current status and future trends of this emerging field.
基金support from the National Natural Science Foundation of China(No.21901206)Postdoctoral Science Foundation of China(No.2022M712589)+2 种基金General Key R&D Projects in Shaanxi Province(No.2023-YBGY-321)Natural Science Foundation of Chongqing(No.CSTB2022NSCQ-MSX0826)National&Local Joint Engineering Research Center for mineral Salt Deep Utilization,Huaiyin Institute of Technology(No.SF202407)for financial support。
文摘The transition metal-catalyzed C–H activation have been considered as increasingly useful approach for installing new functional groups onto organic small molecules due to their high step-and atom-economy,the abundance of hydrocarbon compounds,and the potential for late-stage functionalization of complex organic molecules.The ortho-and meta-C-H activation and functionalization of aromatic compounds have been widely explored in recent years,however the distal para-C-H activation and functionalization has remained a significant challenge because of the difficulty in forming energetically favorable metallacyclic transition states.The utilization of appropriate directing groups or templates as well as the meticulous design of catalysts and ligands has proven to be effective in transition-metal-catalyzed remote para-C-H bonds activation and functionalization of aromatic compounds.This review aims to summarize the strategies for controlling para-selective C–H functionalization using the directing group,template engineering,and catalyst/ligand design under transition metals catalysis in recent years.
基金2024 Special Talent Introduction Projects of Key R&D Program of Ningxia Hui Autonomous Region(2024BEH04049)the 2024 Guyuan City Innovation-Driven Achievement Transformation Project(2024BGTYF01-47)2025 Ningxia Natural Science Foundation Program(2025AAC030624).
文摘Cp_(2)TiCl_(2) as a Lewis acid precursor and nicotinic acid as a ligand have been used synergistically for the one-pot synthesis of 2-(N-substituted amino)-1,4-naphthoquinones.This method establishes a general strategy for the functionalization and conversion of C-H bonds of 1,4-naphthoquinones into C-N bonds,providing an effective route to synthesize 2-(N-substituted amino)-1,4-naphthoquinone with high yield under mild conditions.Additionally,the synergistic catalytic mechanism was investigated by 1H NMR titration experiments and LC-MS analysis,with experimental results sufficiently and consistently supporting the proposed mechanism of the catalytic cycle.
文摘Increased human and industrial activities have exacerbated the release of toxic materials and acute envi-ronmental pollution in recent times.Biochar,a carbon-rich material produced from biomass,is gaining momentum as a versatile material for attaining a sustainable environment.The study reviews the application of functionalized biochar for energy storage,environmental remediation,catalysis,and sustainable agriculture,aiming to achieve a greener future.Thedeployment of crop residues as a renewable feedstock for biochar,and their properties,compositions,modification,and functionalization techniques are also discussed.Additionally,the avenues for applying functionalized biochar to achieve a greener future,future trends and innovations,challenges,and future research directions are highlighted.Despite the limitations of scalability,ecotoxicological risks,logistical issues,lack of characterization protocols,high production costs,poor social acceptance,and inadequate policy and regulatory frameworks,functionalized biochar offers a better surface area,improved porosity,enhanced functional groups,and higher recoverability,leading to improved performance,adsorption capacity,biodegradability,and applications in specialized fields.Future research should prioritize standardization,scalability,cost reduction strategies,expansion of application areas,integration of emerging tools such as artificial intelligence and predictive modeling,and the development of policy and regulatory frameworks,ensuring that biochar’s full potential is harnessed effectively to support a low-carbon,resource-efficient future and global sustainability goals.
文摘In contrast to the predominant mono or difunctionalization of alkenes,the multi-site functionalization of alkenes involving the synergistic formation of more than two new C–C or C–X bonds is much challenging,especially for developing new reaction pathway to afford the functional heterocycle compounds with aggregation-induced emission(AIE)property has been rarely reported.In present work,the multi-site functionalization of in situ generated alkenes with indoles has been developed for the synthesis of diversely functionalized carbazoles through the synergistic construction of multiple C–C bonds and C=O bond.A proposed reaction sequence involving C–H alkenylation/radical oxygen atom transfer/Diels-Alder cycloaddition/dehydrogenative aromatization was supported by experiments and density functional theory calculations.Further derivative carbazole-linked-quinoxaline skeletons represent a class of AIEgens with acceptor-donor-acceptor configuration,which generated the desired twisted intramolecular charge transfer(TICT)AIE properties and could be used as fluorescent probes for detecting the micrometer-sized phase separation of polymer blends.The protocol provides a concise route for the synthesis and application of carbazole-based AIE luminogens.
文摘Purpose: This study focused on maintaining and improving the walking function of late-stage older individuals while longitudinally tracking the effects of regular exercise programs in a day-care service specialized for preventive care over 5 years, using detailed gait function measurements with an accelerometer-based system. Methods: Seventy individuals (17 male and 53 female) of a daycare service in Tokyo participated in a weekly exercise program, meeting 1 - 2 times. The average age of the participants at the start of the program was 81.4 years. Gait function, including gait speed, stride length, root mean square (RMS) of acceleration, gait cycle time and its standard deviation, and left-right difference in stance time, was evaluated every 6 months. Results: Gait speed and stride length improved considerably within six months of starting the exercise program, confirming an initial improvement in gait function. This suggests that regular exercise programs can maintain or improve gait function even age groups that predictably have a gradual decline in gait ability due to enhanced age. In the long term, many indicators tended to approach baseline values. However, the exercise program seemingly counteracts age-related changes in gait function and maintains a certain level of function. Conclusions: While a decline in gait ability with aging is inevitable, establishing appropriate exercise habits in late-stage older individuals may contribute to long-term maintenance of gait function.
基金supported by the National Natural Science Foundation of China,Nos.82072165 and 82272256(both to XM)the Key Project of Xiangyang Central Hospital,No.2023YZ03(to RM)。
文摘Spinal cord injury represents a severe form of central nervous system trauma for which effective treatments remain limited.Microglia is the resident immune cells of the central nervous system,play a critical role in spinal cord injury.Previous studies have shown that microglia can promote neuronal survival by phagocytosing dead cells and debris and by releasing neuroprotective and anti-inflammatory factors.However,excessive activation of microglia can lead to persistent inflammation and contribute to the formation of glial scars,which hinder axonal regeneration.Despite this,the precise role and mechanisms of microglia during the acute phase of spinal cord injury remain controversial and poorly understood.To elucidate the role of microglia in spinal cord injury,we employed the colony-stimulating factor 1 receptor inhibitor PLX5622 to deplete microglia.We observed that sustained depletion of microglia resulted in an expansion of the lesion area,downregulation of brain-derived neurotrophic factor,and impaired functional recovery after spinal cord injury.Next,we generated a transgenic mouse line with conditional overexpression of brain-derived neurotrophic factor specifically in microglia.We found that brain-derived neurotrophic factor overexpression in microglia increased angiogenesis and blood flow following spinal cord injury and facilitated the recovery of hindlimb motor function.Additionally,brain-derived neurotrophic factor overexpression in microglia reduced inflammation and neuronal apoptosis during the acute phase of spinal cord injury.Furthermore,through using specific transgenic mouse lines,TMEM119,and the colony-stimulating factor 1 receptor inhibitor PLX73086,we demonstrated that the neuroprotective effects were predominantly due to brain-derived neurotrophic factor overexpression in microglia rather than macrophages.In conclusion,our findings suggest the critical role of microglia in the formation of protective glial scars.Depleting microglia is detrimental to recovery of spinal cord injury,whereas targeting brain-derived neurotrophic factor overexpression in microglia represents a promising and novel therapeutic strategy to enhance motor function recovery in patients with spinal cord injury.
