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
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
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
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
Although transition metal-catalyzed methylene C(sp^(3))—H functionalization is a great challenge, it has made noticeable progress in recent years. This review specifically describes Pd-catalyzed intermolecular functi...Although transition metal-catalyzed methylene C(sp^(3))—H functionalization is a great challenge, it has made noticeable progress in recent years. This review specifically describes Pd-catalyzed intermolecular functionalization of unactivated methylene C(sp^(3))—H bonds. A variety of reactions, including arylation, alkylation, alkenylation/alkynylation, acetoxylation, amination, halogenation, borylation, and silylation reactions, have been discussed. Due to the inert properties, methylene C(sp^(3))—H functionalization reaction usually relies on the use of directing group strategies, which can not only control regioselectivity but also address low reactivity issue. Various directing groups, including strongly coordinating bidentate auxiliaries and weakly coordinating innate functional groups, have proven to be effective for enabling methylene C(sp^(3))—H functionalization.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
We reported the characterization of a novel brassicicene diterpene biosynthetic gene cluster,which contains a uniqueα-ketoglutarate-dependent dioxygenase(αKGD)enzyme,AbnI.Our findings revealed that AbnI demonstrates...We reported the characterization of a novel brassicicene diterpene biosynthetic gene cluster,which contains a uniqueα-ketoglutarate-dependent dioxygenase(αKGD)enzyme,AbnI.Our findings revealed that AbnI demonstrates remarkable substrate promiscuity and is capable of activating multiple sites on both 5-8-5 and 5-9-5 brassicicene skeletons,resulting in skeleton modifications and an unexpected ring system rearrangement.These results suggested the potential utility of AbnI as an enzymatic tool for terpene C-H functionalization.In addition,the catalytic mechanism of AbnI and its potential ecological implications were discussed.展开更多
The new reactions between o-hydroxyphenyl enaminones and Langlois reagent(CF_(3)SO_(2)Na)for the tunable synthesis of 3-(trifluoromethylthio)chromones and 3-trifluoromethylsulfinyl chromones are reported herein.Both t...The new reactions between o-hydroxyphenyl enaminones and Langlois reagent(CF_(3)SO_(2)Na)for the tunable synthesis of 3-(trifluoromethylthio)chromones and 3-trifluoromethylsulfinyl chromones are reported herein.Both type of reactions proceed under transition metal-free conditions.In addition,the conditions for the synthesis of 3-trifluoromethylsulfinyl chromones have also been found to be applicable for the synthesis of 3-alkyl/arylsulfinyl chromones.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
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
Chemical functionalization of graphene is a topic of paramount importance to broaden its applications in chemistry,physics,and biological science but remains a great challenge due to its low chemical activity and poor...Chemical functionalization of graphene is a topic of paramount importance to broaden its applications in chemistry,physics,and biological science but remains a great challenge due to its low chemical activity and poor dispersion.Here,we report a strategy for the photosynergetic electrochemical functionalization of graphene(EFG).By using chloride ion(Cl^(-))as the intercalation anions and co-reactants,the electrogenerated radicals confined in the expanded graphite layers enable efficient radical addition reaction,thus grasping crystallineperfect EFG.We found that the ultraviolet irradiation and applied voltage have increased the surface/interface concentration of Cl,thus boosting the functionalization of graphene.Theoretical calculation and experimental results verified the oxygen evolution reaction(OER)on EFG has been improved by regulating the doping of chlorine atoms.In addition,the reduced interlayer distance and enhanced electrostatic repulsion near the basal plane endow the fabricated EFG-based membrane with high salt retention.This work highlights a method for the in situ functionalization of graphene and the subsequent applications in OER and water desalination.展开更多
Organofluorines play a crucial role in medicine,agrochemicals,and materials science.Adding fluorine to molecules creates structures with specific beneficial properties or tunes properties through interactions with the...Organofluorines play a crucial role in medicine,agrochemicals,and materials science.Adding fluorine to molecules creates structures with specific beneficial properties or tunes properties through interactions with their environment.Many popular pharmaceuticals and agrochemicals contain fluorine because it enhances hydrogen bonding at protein’s active sites.展开更多
Amino acids are the building blocks of proteins and play vital roles in both biological systems and drug development.In recent years,increasing attention has been given to the functionalization of amino acid derivativ...Amino acids are the building blocks of proteins and play vital roles in both biological systems and drug development.In recent years,increasing attention has been given to the functionalization of amino acid derivatives.Since the introduction of therapeutic insulin in the early 20th century,the conjugation of drug molecules with amino acids and peptides has been pivotal in driving advancements in drug discovery and become an integral part of modern medical practice.Currently,over a hundred peptide-drug conjugates have received global approval and are widely used to treat diseases such as diabetes,cancer,chronic pain,and multiple sclerosis.Key technologies for conjugating peptides with bioactive molecules include antibody-drug conjugates(ADCs),peptide-drug conjugates(PDCs),and proteolysis targeting chimeras(PROTACs).Significant efforts have been dedicated to developing strategies for the modification of amino acids and peptides,with particular focus on site-selective C-H alkylation/arylation reactions.These reactions are crucial for synthesizing bioactive molecules,as they enable the precise introduction of functional groups at specific positions,thereby improving the pharmacological properties of the resulting compounds.展开更多
1-Isoquinolin-1(2H)-one skeleton exists widely in natural products,pharmaceuticals and materials.We disclose here a fluorine effect and catalyst cooperatively induced regioselective or regiospecific 3,4-functionalizat...1-Isoquinolin-1(2H)-one skeleton exists widely in natural products,pharmaceuticals and materials.We disclose here a fluorine effect and catalyst cooperatively induced regioselective or regiospecific 3,4-functionalization of unsymmetric 2-CF_(3)-1,3-enynes.The presence of trifluoromethyl group is determinable for the regioselectivity.When the CF_(3) group was replaced with the methyl or amide group,the regioselectivity decreased to a ratio of 1.3:1 or 1:1.7,respectively.For alkyl substitutedβ-CF_(3)-1,3-enynes,a regiospecificity was obtained.This strategy features excellent regioselectivity,broad substrate scope and high functional group tolerance.Mechanistic studies showed that C–H bond activation is the rate-limiting step.展开更多
In this study,precise control over the thickness and termination of Ti3C2TX MXene flakes is achieved to enhance their electrical properties,environmental stability,and gas-sensing performance.Utilizing a hybrid method...In this study,precise control over the thickness and termination of Ti3C2TX MXene flakes is achieved to enhance their electrical properties,environmental stability,and gas-sensing performance.Utilizing a hybrid method involving high-pressure processing,stirring,and immiscible solutions,sub-100 nm MXene flake thickness is achieved within the MXene film on the Si-wafer.Functionalization control is achieved by defunctionalizing MXene at 650℃ under vacuum and H2 gas in a CVD furnace,followed by refunctionalization with iodine and bromine vaporization from a bubbler attached to the CVD.Notably,the introduction of iodine,which has a larger atomic size,lower electronegativity,reduce shielding effect,and lower hydrophilicity(contact angle:99°),profoundly affecting MXene.It improves the surface area(36.2 cm^(2) g^(-1)),oxidation stability in aqueous/ambient environments(21 days/80 days),and film conductivity(749 S m^(-1)).Additionally,it significantly enhances the gas-sensing performance,including the sensitivity(0.1119Ωppm^(-1)),response(0.2% and 23%to 50 ppb and 200 ppm NO_(2)),and response/recovery times(90/100 s).The reduced shielding effect of the–I-terminals and the metallic characteristics of MXene enhance the selectivity of I-MXene toward NO2.This approach paves the way for the development of stable and high-performance gas-sensing two-dimensional materials with promising prospects for future studies.展开更多
Mercury ion(Hg^(2+)),as one of the most toxic heavy metal ions,accumulates easily in the environment,which can generate potential hazards to the ecosystem and human health.To effectively detect and remove Hg^(2+),we f...Mercury ion(Hg^(2+)),as one of the most toxic heavy metal ions,accumulates easily in the environment,which can generate potential hazards to the ecosystem and human health.To effectively detect and remove Hg^(2+),we fabricated four types of carbon dots(CDs)using carboxymethyl nanocellulose as a carbon source doped with different elements using a hydrothermal method.All the CDs exhibited a strong fluorescence emission,excitation-dependent emission and possessed good water dispersibility.Moreover,the four fluorescent CDs were used for Hg^(2+)recognition in aqueous solution,where the CDs-N exhibited better sensitivity and selectivity for Hg^(2+)detection,with a low limit of detection of 8.29×10^(-6)mol/L.It was determined that the fluorescence quenching could be ascribed to a photoinduced charge-transfer processes between Hg^(2+)and the CDs.In addition,the CDs-N were used as a smart invisible ink for anticounterfeiting,information encryption and decryption.Furthermore,the CDs-N were immersed into a cellulose(CMC)-based hydrogel network to prepare fluorescent hydrogels capable of simultaneously detecting and adsorbing Hg^(2+).We anticipate that this research will open possibilities for a green method to synthesize fluorescent CDs for metal ion detection and fluorescent ink production.展开更多
Silver-catalyzed decarboxylative C–H alkylation of cyclic aldimines with abundant aliphatic carboxylic acids has been realized under mild reaction conditions generating the corresponding products in moderate to good ...Silver-catalyzed decarboxylative C–H alkylation of cyclic aldimines with abundant aliphatic carboxylic acids has been realized under mild reaction conditions generating the corresponding products in moderate to good yields(32%–91%).In addition,a gram-scale reaction,late-stage modification of drug,synthetic transformation of the product,and further application of the catalytic strategy were also performed.Preliminary studies indicate that the reaction undergoes a radical process.展开更多
Herein, a site-selective paired electrochemical C–H oxidation of functionalized alkyl arenes promoted by nickel catalyst is disclosed. A Ni(Ⅱ)-dioxygen species formed in situ efficiently enable the oxidation process...Herein, a site-selective paired electrochemical C–H oxidation of functionalized alkyl arenes promoted by nickel catalyst is disclosed. A Ni(Ⅱ)-dioxygen species formed in situ efficiently enable the oxidation process under mild conditions with a broad substrate scope with excellent functional group compatibilities,such as free carboxylic acid, aldehyde, halogen(including aryl iodide), amide and amino acid. The use of the nickel catalyst in combination with water provides a safe, green and economical method for oxidation of a range of molecules varying in complexity and drug derivatives, demonstrating its potential application in organic synthesis and the pharmaceutical industry. Reaction outcomes and mechanistic studies revealed the key role of the in situ Ni(Ⅱ)-dioxygen species for the subsequent oxidation of C(sp^(3))–H bonds,and short-lived reactive intermediates(aryl radical cation) was rapidly captured by the combination of a bipolar ultramicroelectrode(BUME) with nano-electrospray ionization mass spectrometry.展开更多
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.
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.
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.
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.
文摘Although transition metal-catalyzed methylene C(sp^(3))—H functionalization is a great challenge, it has made noticeable progress in recent years. This review specifically describes Pd-catalyzed intermolecular functionalization of unactivated methylene C(sp^(3))—H bonds. A variety of reactions, including arylation, alkylation, alkenylation/alkynylation, acetoxylation, amination, halogenation, borylation, and silylation reactions, have been discussed. Due to the inert properties, methylene C(sp^(3))—H functionalization reaction usually relies on the use of directing group strategies, which can not only control regioselectivity but also address low reactivity issue. Various directing groups, including strongly coordinating bidentate auxiliaries and weakly coordinating innate functional groups, have proven to be effective for enabling methylene C(sp^(3))—H functionalization.
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.
基金financially supported by the National Key R&D Program of China(Nos.2021YFA0910500,2021YFA0910503)the National Natural Science Foundation of China(Nos.22277035,32000045 and 81973205)+4 种基金the Program for Changjiang Scholars of Ministry of Education of the People’s Republic of China(No.T2016088)the National Natural Science Foundation for Distinguished Young Scholars(No.81725021)the National Science and Technology Project of China(No.2018ZX09201001-001-003)Innovative Research Groups of the National Natural Science Foundation of China(No.81721005)the Fundamental Research Funds for the Central Universities(No.2020kfyXJJS043).
文摘We reported the characterization of a novel brassicicene diterpene biosynthetic gene cluster,which contains a uniqueα-ketoglutarate-dependent dioxygenase(αKGD)enzyme,AbnI.Our findings revealed that AbnI demonstrates remarkable substrate promiscuity and is capable of activating multiple sites on both 5-8-5 and 5-9-5 brassicicene skeletons,resulting in skeleton modifications and an unexpected ring system rearrangement.These results suggested the potential utility of AbnI as an enzymatic tool for terpene C-H functionalization.In addition,the catalytic mechanism of AbnI and its potential ecological implications were discussed.
基金financially supported by National Natural Science Foundation of China(No.22161022)。
文摘The new reactions between o-hydroxyphenyl enaminones and Langlois reagent(CF_(3)SO_(2)Na)for the tunable synthesis of 3-(trifluoromethylthio)chromones and 3-trifluoromethylsulfinyl chromones are reported herein.Both type of reactions proceed under transition metal-free conditions.In addition,the conditions for the synthesis of 3-trifluoromethylsulfinyl chromones have also been found to be applicable for the synthesis of 3-alkyl/arylsulfinyl chromones.
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.
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.
基金supported by the Natural Science Foundation of Guangxi Province(2021GXNSFBA220077,GUIKE AD23026050)National Natural Science Foundation of China(22102035 and 22162006)Innovation Project of Guangxi Graduate Education(XYCBZ2024021).
文摘Chemical functionalization of graphene is a topic of paramount importance to broaden its applications in chemistry,physics,and biological science but remains a great challenge due to its low chemical activity and poor dispersion.Here,we report a strategy for the photosynergetic electrochemical functionalization of graphene(EFG).By using chloride ion(Cl^(-))as the intercalation anions and co-reactants,the electrogenerated radicals confined in the expanded graphite layers enable efficient radical addition reaction,thus grasping crystallineperfect EFG.We found that the ultraviolet irradiation and applied voltage have increased the surface/interface concentration of Cl,thus boosting the functionalization of graphene.Theoretical calculation and experimental results verified the oxygen evolution reaction(OER)on EFG has been improved by regulating the doping of chlorine atoms.In addition,the reduced interlayer distance and enhanced electrostatic repulsion near the basal plane endow the fabricated EFG-based membrane with high salt retention.This work highlights a method for the in situ functionalization of graphene and the subsequent applications in OER and water desalination.
文摘Organofluorines play a crucial role in medicine,agrochemicals,and materials science.Adding fluorine to molecules creates structures with specific beneficial properties or tunes properties through interactions with their environment.Many popular pharmaceuticals and agrochemicals contain fluorine because it enhances hydrogen bonding at protein’s active sites.
文摘Amino acids are the building blocks of proteins and play vital roles in both biological systems and drug development.In recent years,increasing attention has been given to the functionalization of amino acid derivatives.Since the introduction of therapeutic insulin in the early 20th century,the conjugation of drug molecules with amino acids and peptides has been pivotal in driving advancements in drug discovery and become an integral part of modern medical practice.Currently,over a hundred peptide-drug conjugates have received global approval and are widely used to treat diseases such as diabetes,cancer,chronic pain,and multiple sclerosis.Key technologies for conjugating peptides with bioactive molecules include antibody-drug conjugates(ADCs),peptide-drug conjugates(PDCs),and proteolysis targeting chimeras(PROTACs).Significant efforts have been dedicated to developing strategies for the modification of amino acids and peptides,with particular focus on site-selective C-H alkylation/arylation reactions.These reactions are crucial for synthesizing bioactive molecules,as they enable the precise introduction of functional groups at specific positions,thereby improving the pharmacological properties of the resulting compounds.
基金supported by National Natural Science Founda:tion of China(22461002,22308061,22305046)Natural Science Foundation(NSF)of Jiangxi Province(20224BAB213011,20242BAB20110,20224BAB213012)+1 种基金High-Level and Highly Demanded Overseas Talent Programs of Jiangxi Province(20232BCJ25050)Gannan Normal University Start-up Fund(BSJJ202109).
文摘1-Isoquinolin-1(2H)-one skeleton exists widely in natural products,pharmaceuticals and materials.We disclose here a fluorine effect and catalyst cooperatively induced regioselective or regiospecific 3,4-functionalization of unsymmetric 2-CF_(3)-1,3-enynes.The presence of trifluoromethyl group is determinable for the regioselectivity.When the CF_(3) group was replaced with the methyl or amide group,the regioselectivity decreased to a ratio of 1.3:1 or 1:1.7,respectively.For alkyl substitutedβ-CF_(3)-1,3-enynes,a regiospecificity was obtained.This strategy features excellent regioselectivity,broad substrate scope and high functional group tolerance.Mechanistic studies showed that C–H bond activation is the rate-limiting step.
基金supported by the National Research Foundation of Korea (NRF) grant funded by the Korean government (MSIT)(No. 2021R1I1A1A0105621313, No. 2022R1F1A1074441, No. 2022K1A3A1A20014496, and No. 2022R1F1A1074083)supported by the Ministry of Education Funding (No. RIS 2021-004)supported by the Brain Pool program funded by the Ministry of Science and ICT through the National Research Foundation of Korea (RS-2023-00284318).
文摘In this study,precise control over the thickness and termination of Ti3C2TX MXene flakes is achieved to enhance their electrical properties,environmental stability,and gas-sensing performance.Utilizing a hybrid method involving high-pressure processing,stirring,and immiscible solutions,sub-100 nm MXene flake thickness is achieved within the MXene film on the Si-wafer.Functionalization control is achieved by defunctionalizing MXene at 650℃ under vacuum and H2 gas in a CVD furnace,followed by refunctionalization with iodine and bromine vaporization from a bubbler attached to the CVD.Notably,the introduction of iodine,which has a larger atomic size,lower electronegativity,reduce shielding effect,and lower hydrophilicity(contact angle:99°),profoundly affecting MXene.It improves the surface area(36.2 cm^(2) g^(-1)),oxidation stability in aqueous/ambient environments(21 days/80 days),and film conductivity(749 S m^(-1)).Additionally,it significantly enhances the gas-sensing performance,including the sensitivity(0.1119Ωppm^(-1)),response(0.2% and 23%to 50 ppb and 200 ppm NO_(2)),and response/recovery times(90/100 s).The reduced shielding effect of the–I-terminals and the metallic characteristics of MXene enhance the selectivity of I-MXene toward NO2.This approach paves the way for the development of stable and high-performance gas-sensing two-dimensional materials with promising prospects for future studies.
基金supported by the National Natural Science Foundation of China(Nos.52370110 and 21607044)supported by the Fundamental Research Funds for the Central Universities(No.2023MS146)the Open Research Fund of the School of Chemistry and Chemical Engineering,Henan Normal University for support(Nos.2020ZD01 and 2021YB07)。
文摘Mercury ion(Hg^(2+)),as one of the most toxic heavy metal ions,accumulates easily in the environment,which can generate potential hazards to the ecosystem and human health.To effectively detect and remove Hg^(2+),we fabricated four types of carbon dots(CDs)using carboxymethyl nanocellulose as a carbon source doped with different elements using a hydrothermal method.All the CDs exhibited a strong fluorescence emission,excitation-dependent emission and possessed good water dispersibility.Moreover,the four fluorescent CDs were used for Hg^(2+)recognition in aqueous solution,where the CDs-N exhibited better sensitivity and selectivity for Hg^(2+)detection,with a low limit of detection of 8.29×10^(-6)mol/L.It was determined that the fluorescence quenching could be ascribed to a photoinduced charge-transfer processes between Hg^(2+)and the CDs.In addition,the CDs-N were used as a smart invisible ink for anticounterfeiting,information encryption and decryption.Furthermore,the CDs-N were immersed into a cellulose(CMC)-based hydrogel network to prepare fluorescent hydrogels capable of simultaneously detecting and adsorbing Hg^(2+).We anticipate that this research will open possibilities for a green method to synthesize fluorescent CDs for metal ion detection and fluorescent ink production.
基金financially supported by the National Natural Science Foundation of China(Nos.21402116,21502111,21572126)the Science and Technology Innovation Talents of Henan Province(No.2018JQ0011)the Key Science Research of Education Committee in Henan Province(No.21A150044)。
文摘Silver-catalyzed decarboxylative C–H alkylation of cyclic aldimines with abundant aliphatic carboxylic acids has been realized under mild reaction conditions generating the corresponding products in moderate to good yields(32%–91%).In addition,a gram-scale reaction,late-stage modification of drug,synthetic transformation of the product,and further application of the catalytic strategy were also performed.Preliminary studies indicate that the reaction undergoes a radical process.
基金Financial support from National Key R&D Program of China(No.2022YFA1503200)National Natural Science Foundation of China(No.22188101)+1 种基金the Fundamental Research Funds for the Central Universities(No.63223007)Frontiers Science Center for New Organic Matter,Nankai University(No.63181206)and Nankai University.
文摘Herein, a site-selective paired electrochemical C–H oxidation of functionalized alkyl arenes promoted by nickel catalyst is disclosed. A Ni(Ⅱ)-dioxygen species formed in situ efficiently enable the oxidation process under mild conditions with a broad substrate scope with excellent functional group compatibilities,such as free carboxylic acid, aldehyde, halogen(including aryl iodide), amide and amino acid. The use of the nickel catalyst in combination with water provides a safe, green and economical method for oxidation of a range of molecules varying in complexity and drug derivatives, demonstrating its potential application in organic synthesis and the pharmaceutical industry. Reaction outcomes and mechanistic studies revealed the key role of the in situ Ni(Ⅱ)-dioxygen species for the subsequent oxidation of C(sp^(3))–H bonds,and short-lived reactive intermediates(aryl radical cation) was rapidly captured by the combination of a bipolar ultramicroelectrode(BUME) with nano-electrospray ionization mass spectrometry.
