Heterocyclic ketene aminals 1 react with aryl azides 2 to give the titled compounds 3,and in some cases also with the formation of fused heterocycles 4.
An efficient solid-phase synthesis method for novel heterocyclic ketene aminals containing a hydroxyl group has been developed. The loading of the substrate on the resin through the hydroxyl group and the protection o...An efficient solid-phase synthesis method for novel heterocyclic ketene aminals containing a hydroxyl group has been developed. The loading of the substrate on the resin through the hydroxyl group and the protection of the amine by the Schiff base were the key steps in the synthesis.展开更多
Heteroatom aroyl-substituted heterocyclic ketene aminals 1 reacted with 2,3,4,6-tetra-O-acetyl-α-glucopyranosyl bromide 2 under the catalysis of Hg(CN)2 or CaH2 to give E- or Z-O-glycosides of heterocyclic ketene am...Heteroatom aroyl-substituted heterocyclic ketene aminals 1 reacted with 2,3,4,6-tetra-O-acetyl-α-glucopyranosyl bromide 2 under the catalysis of Hg(CN)2 or CaH2 to give E- or Z-O-glycosides of heterocyclic ketene aminals 3 or 4 in moderate yields.展开更多
The anion of heterocyclic ketene aminals reacted with 2,4-dini- tro-halobenzenes to give an arylated product through the radical nucleo- philic substitution confirmed by ESR spectroscopy,ESR-spin trapping techni- que,...The anion of heterocyclic ketene aminals reacted with 2,4-dini- tro-halobenzenes to give an arylated product through the radical nucleo- philic substitution confirmed by ESR spectroscopy,ESR-spin trapping techni- que,and depression of the reaction rate by the addition of inhibitor.展开更多
Summary of main observation and conclusion A 4+2 cycloaddition reaction of NH-free benzazetidines with indoles under the catalysis of camphorsulfonic acid was developed. This method shows a broad substrate scope of be...Summary of main observation and conclusion A 4+2 cycloaddition reaction of NH-free benzazetidines with indoles under the catalysis of camphorsulfonic acid was developed. This method shows a broad substrate scope of benzazetidines and indoles, and offers a convenient method for stereoselective synthesis of various cis-2,3-fused indoline aminals. Preliminary mechanistic studies suggest the reaction proceed via a stepwise pathway featuring an electrophilic attack on the benzylic carbon of benzazetidine.展开更多
Monitoring biogenic amines,which are metabolic byproducts of shrimp spoilage,is crucial for assessing food quality.Currently,most detection methods for biogenic amines suffer from limitations such as time-consuming pr...Monitoring biogenic amines,which are metabolic byproducts of shrimp spoilage,is crucial for assessing food quality.Currently,most detection methods for biogenic amines suffer from limitations such as time-consuming procedures,complex operations,and delayed results.Colorimetric analysis techniques have gained attention in recent years due to their advantages of short analysis time,simple operation,and suitability for on-site testing.This study successfully developed a series of colorimetric sensor platforms for biogenic amines by loading the natural active ingredient curcumin(CUR)and its derivative of Boron complex BFCUR onto filter paper and electrospun nanofibre films(ENFs),respectively.By analyzing the color response differences of these sensors upon contact with biogenic amines,the colorimetric sensors with superior detection performance were selected and further applied to the visual monitoring and indication of shrimp spoilage processes.展开更多
Chiral benzylic amines are important motifs in medicines.A dicationic nickel complex of chiral diphosphine(R)-Ph-BPE promotes highly enantioselective reductive amination of aryl alkyl ketones with arylamines using iso...Chiral benzylic amines are important motifs in medicines.A dicationic nickel complex of chiral diphosphine(R)-Ph-BPE promotes highly enantioselective reductive amination of aryl alkyl ketones with arylamines using isopropanol as hydrogen source.The reaction is easily scaled up in a gram-scale synthesis using 1 mol% nickel catalyst and it is applied to an asymmetric synthesis of(S)-rivastigmine.Building on this success,we achieved rare examples of asymmetric hydrogen borrowing reactions with arylamines using an Earth-abundant 3d metal,nickel.展开更多
Nitrogen-containing structures represent a significant branch exhibiting remarkable biological activity,surpassing non-nitrogen architectures.Given the vast array of nitrogen-containing compounds and their crucial rol...Nitrogen-containing structures represent a significant branch exhibiting remarkable biological activity,surpassing non-nitrogen architectures.Given the vast array of nitrogen-containing compounds and their crucial role in the pharmaceutical industry,chemists have been motivated to devise efficient,cost-effective,and practical methods for C-N bond formation.Significant advancements have been achieved in this cutting-edge field over the past few decades.This review aims to encapsulate the latest progress in C-N bond formation via the photocatalytic C-H amination process.Initially,we provide a comprehensive introduction to C-H amination transformations.Subsequently,we categorize these photochemical conversions into two parts:intramolecular and intermolecular C-H amination.To elucidate the underlying principles of specific illustrative examples,we have carefully chosen and elaborated on the reaction mechanisms,representative experimental outcomes,and applications.展开更多
Aqueous zinc-based batteries have emerged as promising candidates for large-scale energy storage owing to their inherent safety and cost-effectiveness.However,their widespread application is impeded by dendritic forma...Aqueous zinc-based batteries have emerged as promising candidates for large-scale energy storage owing to their inherent safety and cost-effectiveness.However,their widespread application is impeded by dendritic formation and parasitic reactions at zinc anodes.To address these issues,this study employs polyethyleneimine grafting and macropore filling to synergistically modify the cellulose separator.The zincophilic–NH_(2) and–NH–groups introduced by polyethyleneimine promote Zn^(2+)ion desolvation and nucleation processes.Concurrently,the nanocellulose incorporated into macropores not only significantly enhances mechanical properties but also compensates for macroporous defects within the cellulose separator.The optimized separator exhibits ultralow thickness(18μm),ultrahigh modulus(3.2 GPa),large ionic conductivity(19.0 mS cm^(-1)),high Zn^(2+)ion transfer number(0.63),and good biodegradability.Comprehensive experimental measurements and theoretical analysis reveal that the utilization of this separator contributes to significantly suppressed zinc dendrites and improved electrochemical kinetics.The assembled Zn//Zn cell demonstrates exceptional cycling stability(over 1000 h lifespan at10 m A cm^(-2)and 2 mAh cm^(-2)),and the Zn//MnO_(2) and Zn//I_(2) full batteries maintain excellent longterm cyclability under high cathode mass loadings.This work advances our understanding of multifunctional separator design for next-generation electrochemical energy storage systems.展开更多
This study investigated the suppressive effects of Armoracia rusticana(AR)and its three main glucosinolates on both free and bound heterocyclic amines(HAs),along with their mechanisms of free radical quenching using d...This study investigated the suppressive effects of Armoracia rusticana(AR)and its three main glucosinolates on both free and bound heterocyclic amines(HAs),along with their mechanisms of free radical quenching using density functional theory.Fish patties were supplemented with varying concentrations of AR(0.5%‒1.5%)and glucosinolates(0.005%‒0.015%),showing a dose-dependent inhibition of HAs and concurrent elimination of free radicals and HAs intermediates.Glucobrassicin demonstrated the highest reactivity,which was verified by frontier orbit analysis and conceptual density functional parameters,consistent with experimental findings.Furthermore,the O-H bond connected to the sulfur atom of glucobrassicin possessed the smallest bond dissociation enthalpy(BDE)value,which indicated that this particular hydrogen atom is most susceptible to react with free radicals.Overall,AR and its glucosinolates,especially glucobrassicin,show promise as natural additives for improving food safety and quality.展开更多
The widespread use of herbicides such as glyphosate isopropyl amine salt(GIS)and atrazine(ATZ)poses significant risks to aquatic ecosystems.This study investigated the single and joint acute toxicity of a 1:1 GIS-ATZ ...The widespread use of herbicides such as glyphosate isopropyl amine salt(GIS)and atrazine(ATZ)poses significant risks to aquatic ecosystems.This study investigated the single and joint acute toxicity of a 1:1 GIS-ATZ mixture on zebrafish(Danio rerio).Acute tests determined 96-h LC_(50) values of 123.41 mg/L for GIS and 103.95 mg/L for ATZ.In the joint toxicity test,these values decreased to 60.96 and 50.88 mg/L,respectively.The Additive Index(AI)analysis revealed a consistent synergistic interaction between the herbicides at all exposure intervals.These findings underscore the enhanced ecological threat of herbicide mixtures and highlight the necessity of considering joint effects in environmental risk assessments.展开更多
The application of poly(butylene adipate-co-terephthalate)(PBAT)biodegradable plastics has long been constrained by insufficient light aging resistance.Hindered amine light stabilizers(HALSs),known as eco-friendly add...The application of poly(butylene adipate-co-terephthalate)(PBAT)biodegradable plastics has long been constrained by insufficient light aging resistance.Hindered amine light stabilizers(HALSs),known as eco-friendly additives,can scavenge free radicals to enhance polymer durability.However,rough choices have resulted in wastage of resources and environmental pressure.Based on the application of plastic films as the background for use,this study systematically evaluates application effects of five HALSs.The films underwent accelerated aging for various durations and were further investigated by a combination of experiments and molecular simulation.Results showed that all HALSs mitigated PBAT light aging,with Chimassorb-944(UV-944)and Tinuvin-770(UV-770)performing the best for real applications.Quantum chemical calculation results showed that UV-944 had stronger anti migration ability.After 300 h of aging,films with UV-944 and UV-770 retained superior tensile strength and elongation at break in the transverse direction compared to neat PBAT films.Polymeric HALSs provided better long-term stability than small-molecule ones.Further spectra analysis indicated that stronger C―O bonds in HALS/PBAT composites correlated with improved photostability.This study offers valuable insights into improving weather resistance of PBAT biodegradable films and optimizing the real application of HALSs.展开更多
A new palladium-catalyzed selective aminomethylation of conjugated 1,3-dienes with aminais via double C-N bond activation is described. This simple method provides an effective and rapid approach for the synthesis of ...A new palladium-catalyzed selective aminomethylation of conjugated 1,3-dienes with aminais via double C-N bond activation is described. This simple method provides an effective and rapid approach for the synthesis of linear a,13-unsaturated allylic amines with perfect regioselectivity. Mechanistic studies disclosed that one palladium catalyst cleaved two distinct C-N bond to furnish a cascade double C-N bond activation, in which an allylic 1,3-diamine and allylic 1,2-diamine were initially formed as key intermediates through the palladium-catalyzed C-N bond activation of aminal and the α,β-unsaturated allylic amine was subsequently produced via palladium-catalyzed C-N bond activation of the allylic diamines.展开更多
The stereoselective synthesis of O-maltosides by reacting benzoyl-substituted heterocyclic ketene aminals 1 or 2 with acetylated maltosyl bromide 3 was investigated. Compounds 1 or 2 reacted with 3 in the presence of ...The stereoselective synthesis of O-maltosides by reacting benzoyl-substituted heterocyclic ketene aminals 1 or 2 with acetylated maltosyl bromide 3 was investigated. Compounds 1 or 2 reacted with 3 in the presence of mercuric cyanide to give O-maltosides 4 or 5 with E-configuration. While 1 reacted with 3 in the presence of calcium hydride to give O-maltosides 6 with Z-configuration.展开更多
Heterogeneous metal-catalyzed chemical conversions with a recyclable catalyst are very ideal and challenging for sustainable organic synthesis.A new bipyridyl-Mo(IV)-carbon nitride(CN-K/Mo-Bpy)was prepared by supporti...Heterogeneous metal-catalyzed chemical conversions with a recyclable catalyst are very ideal and challenging for sustainable organic synthesis.A new bipyridyl-Mo(IV)-carbon nitride(CN-K/Mo-Bpy)was prepared by supporting molybdenum complex on C_(3)N_(4)-K and characterized by FT-IR,XRD,SEM,XPS and ICP-OES.Heterogeneous CN–Mo-Bpy catalyst can be applied to the direct amination of nitroarenes and arylboronic acid,thus constructing various valuable diarylamines in high to excellent yields with a wide substrate scope and good functional group tolerance.It is worth noting that this heterogeneous catalyst has high chemical stability and can be recycled for at least five times without reducing its activity.展开更多
In-depth knowledge of the microbes responsible for biogenic amine(BA)production during soy sauce fermentation remains limited.Herein,the variations in the BA profiles,microbial communities,and microbes involved in BA ...In-depth knowledge of the microbes responsible for biogenic amine(BA)production during soy sauce fermentation remains limited.Herein,the variations in the BA profiles,microbial communities,and microbes involved in BA production during the fermentation of soy sauce through Japanese-type(JP)and Cantonese-type(CP)processes were compared.BA analysis revealed that the most abundant BA species were putrescine,tyramine,and histamine in the later three stages(1187.68,785.16,and 193.20 mg/kg on average,respectively).The BA profiles differed significantly,with CP samples containing higher contents of putrescine,tyramine,and histamine(P<0.05)at the end of fermentation.Metagenomic analysis indicated that BA-producing genes exhibited different abundance profiles,with most genes,including spe A,spe B,arg,spe E,and tyr DC,having higher abundances in microbial communities during the CP process.In total,15 high-quality metagenome-assembled genomes(MAGs)were retrieved,of which 10 encoded at BA production-related genes.Enterococcus faecium(MAG10)and Weissella paramesenteroides(MAG5)might be the major tyramine producers.The high putrescine content in CP might be associated with the high abundance of Staphylococcus gallinarum(MAG8).This study provides a comprehensive understanding of the diversity and abundance of genes involved in BA synthesis,especially at the species level,during food fermentation.展开更多
Nitrogenous compounds(i.e.,amines,amides,nitriles,oximes,amino acids and nitrogen-heterocycles derivatives)are important building blocks for synthetic chemistry,pharmaceuticals,and functional materials.Conventional sy...Nitrogenous compounds(i.e.,amines,amides,nitriles,oximes,amino acids and nitrogen-heterocycles derivatives)are important building blocks for synthetic chemistry,pharmaceuticals,and functional materials.Conventional synthetic strategies involve the use of toxic organic nitrogenous precursors or expensive heterogeneous catalysts under elevated temperatures and pressurized oxygen.Heterogeneous electrocatalysis can initiate the activation of inorganic N sources(i.e.,NH_(3)and NO^(-)_(x))under ambient reactions in liquid phase by applying a small bias,thus allowing the synthesis of value?added nitrogenous compounds from carbonyls,alkenes,keto acids,and even carbon dioxide in a sustainable manner without the use of oxidants/reductants.This review outlines recent de-velopments in electrosynthesis of nitrogenous compounds using inorganic N sources,focusing on reaction mechanisms understanding,the design and optimization of efficient electrocatalysts,and the advances in cell configurations for various C‒N coupling reactions.The limitations and challenges in applications are also discussed.展开更多
Catalyst-aided regeneration is a promising method for reducing the high regeneration energy consumption of amine-based CO_(2)capture technologies.However,the intrinsic relationship between the properties of the acidic...Catalyst-aided regeneration is a promising method for reducing the high regeneration energy consumption of amine-based CO_(2)capture technologies.However,the intrinsic relationship between the properties of the acidic sites and their catalytic activity is controversial.In this study,a series of W-based catalysts supported by ZrTiO_(x)were synthesised,and the effects of the intensity,distribution,and type of acid sites were systematically investigated by quantitatively regulating the acidic site properties.The results indicate stronger acidic sites play a more important role in the catalytic reaction.Moreover,the catalysts showed excellent performance only if the Br?nsted acid sites(BASs)and Lewis acid sites(LASs)coexisted.During the catalytic reaction,the BASs facilitated deprotonation,and the LASs promoted the decomposition of carbamates.The ratio of BASs to LASs(B/L)was a critical factor for catalytic activity,wherein optimal performance was achieved when the B/L ratio was close to 1.The 10%HPW/ZrTiO_(x)composite performed better than WO_(3)/ZrTiO_(x)and HSiW/ZrTiO_(x)because it had a stronger acid intensity and a suitable B/L ratio.As a result,the relative heat duty was reduced by 47%compared to 30%aqueous MEA,and the maximum CO_(2)desorption rate was increased by 83%.The Bader charge indicated that the W atoms of HPW/ZrTiO_(x)lost more electrons(0.18)than those of WO_(3)/ZrTiO_(x),which can weaken the O±H bond energy.Consequently,the calculated deprotonation energy is as low as 257 kJ mol^(-1)for HPW/ZrTiO_(x).展开更多
Isothiocyanates(ITCs)are an important class of organic compounds characterized by the functional group R-N=C=S.These functional groups are widely found in multiple natural products and pharmaceutical important drugs.M...Isothiocyanates(ITCs)are an important class of organic compounds characterized by the functional group R-N=C=S.These functional groups are widely found in multiple natural products and pharmaceutical important drugs.Moreover,due to their high and versatile reactivity,they are widely used as an intermediate in organic synthesis.Keeping in view ITCs importance,this review summarizes their synthesis from nitrogen rich raw materials like amines,isocyanides,azides and some other compounds like oximes.Besides their synthesis,their application in organic compound synthesis as an intermediate will also be covered.Future research will likely focus on optimizing the synthesis of multifunctional isothiocyanates,understanding their complex biological mechanisms,exploring new applications,and highlighting the continued importance of isothiocyanates in modern chemistry and biotechnology.展开更多
文摘Heterocyclic ketene aminals 1 react with aryl azides 2 to give the titled compounds 3,and in some cases also with the formation of fused heterocycles 4.
文摘An efficient solid-phase synthesis method for novel heterocyclic ketene aminals containing a hydroxyl group has been developed. The loading of the substrate on the resin through the hydroxyl group and the protection of the amine by the Schiff base were the key steps in the synthesis.
文摘Heteroatom aroyl-substituted heterocyclic ketene aminals 1 reacted with 2,3,4,6-tetra-O-acetyl-α-glucopyranosyl bromide 2 under the catalysis of Hg(CN)2 or CaH2 to give E- or Z-O-glycosides of heterocyclic ketene aminals 3 or 4 in moderate yields.
文摘The anion of heterocyclic ketene aminals reacted with 2,4-dini- tro-halobenzenes to give an arylated product through the radical nucleo- philic substitution confirmed by ESR spectroscopy,ESR-spin trapping techni- que,and depression of the reaction rate by the addition of inhibitor.
基金financial supported by National Natural Science Foundation of China(No.21372079)National High Technology Research Development Program of China(863 Program,No. 2011AA10A207)+3 种基金Shanghai Pujiang Program(No.14PJD012)Key Projects in the National Science & Technology Pillar Program(No. 2011BAE06B05)the Fundamental Research Funds for the Central Universitiespartly supported by Australia DC Foundation
文摘An efficient synthetic pathway to 2-oxo-1,2-dihydropyridine-fused 1,3-diaza heterocycles from heterocyclic ketene aminals,phathalic anhydride and ethyl cyanacetate was established.This protocol involved aza-ene reaction/imine-enamine tautomerization/enamine-ester exchange/ring-opening reaction sequence.
基金the National Natural Science Foundation of China (Nos. 21502098, 21672105)the Natural Science Foundation of Tianjin (17JCYBJC19700)the Qindao National Laboratory for Marine Scie nee and Tech no logy, and the State Key Laboratory of Elemento-Organic Chemistry at Nankai University for financial support of this work.
文摘Summary of main observation and conclusion A 4+2 cycloaddition reaction of NH-free benzazetidines with indoles under the catalysis of camphorsulfonic acid was developed. This method shows a broad substrate scope of benzazetidines and indoles, and offers a convenient method for stereoselective synthesis of various cis-2,3-fused indoline aminals. Preliminary mechanistic studies suggest the reaction proceed via a stepwise pathway featuring an electrophilic attack on the benzylic carbon of benzazetidine.
基金Supported by the Guangdong-Hong Kong-Macao Joint Laboratory on Micro-Nano Manufacturing Technology,China(No.2021LSYS004)Guangdong Provincial Key Laboratory of Sustainable Biomimetic Materials and Green Energy,China(No.2024B1212010003)。
文摘Monitoring biogenic amines,which are metabolic byproducts of shrimp spoilage,is crucial for assessing food quality.Currently,most detection methods for biogenic amines suffer from limitations such as time-consuming procedures,complex operations,and delayed results.Colorimetric analysis techniques have gained attention in recent years due to their advantages of short analysis time,simple operation,and suitability for on-site testing.This study successfully developed a series of colorimetric sensor platforms for biogenic amines by loading the natural active ingredient curcumin(CUR)and its derivative of Boron complex BFCUR onto filter paper and electrospun nanofibre films(ENFs),respectively.By analyzing the color response differences of these sensors upon contact with biogenic amines,the colorimetric sensors with superior detection performance were selected and further applied to the visual monitoring and indication of shrimp spoilage processes.
基金supported by the National Natural Science Foundation of China(Nos.22271007,W2431014)Peking University Shenzhen Graduate School+2 种基金State Key Laboratory of Chemical OncogenomicsShenzhen Key Laboratory of Chemical GenomicsShenzhen Bay Laboratory.
文摘Chiral benzylic amines are important motifs in medicines.A dicationic nickel complex of chiral diphosphine(R)-Ph-BPE promotes highly enantioselective reductive amination of aryl alkyl ketones with arylamines using isopropanol as hydrogen source.The reaction is easily scaled up in a gram-scale synthesis using 1 mol% nickel catalyst and it is applied to an asymmetric synthesis of(S)-rivastigmine.Building on this success,we achieved rare examples of asymmetric hydrogen borrowing reactions with arylamines using an Earth-abundant 3d metal,nickel.
基金funded by the National Natural Science Foundation of China(Nos.82103686 and 22101267)the China Postdoctoral Science Foundation(No.2021M692905 and 2024T170832)Natural Science Foundation of Henan Province(242300421123).
文摘Nitrogen-containing structures represent a significant branch exhibiting remarkable biological activity,surpassing non-nitrogen architectures.Given the vast array of nitrogen-containing compounds and their crucial role in the pharmaceutical industry,chemists have been motivated to devise efficient,cost-effective,and practical methods for C-N bond formation.Significant advancements have been achieved in this cutting-edge field over the past few decades.This review aims to encapsulate the latest progress in C-N bond formation via the photocatalytic C-H amination process.Initially,we provide a comprehensive introduction to C-H amination transformations.Subsequently,we categorize these photochemical conversions into two parts:intramolecular and intermolecular C-H amination.To elucidate the underlying principles of specific illustrative examples,we have carefully chosen and elaborated on the reaction mechanisms,representative experimental outcomes,and applications.
基金the financial support from the Natural Science Foundation of Jiangsu Province(BK20231292)the Jiangsu Agricultural Science and Technology Innovation Fund(CX(24)3091)+7 种基金the National Key R&D Program of China(2024YFE0109200)the Fundamental Research Funds for the Central Universities(No.2024300440)the Guangdong Basic and Applied Basic Research Foundation(2025A1515011098)the Postgraduate Research&Practice Innovation Program of Jiangsu Province(KYCX24_1299)the National Natural Science Foundation of China(12464032)the Natural Science Foundation of Jiangxi Province(20232BAB201032)the Ji’an Science and Technology Plan Project(2024H-100301)supported by the high-performance computing campus level public platform of Jinggangshan University。
文摘Aqueous zinc-based batteries have emerged as promising candidates for large-scale energy storage owing to their inherent safety and cost-effectiveness.However,their widespread application is impeded by dendritic formation and parasitic reactions at zinc anodes.To address these issues,this study employs polyethyleneimine grafting and macropore filling to synergistically modify the cellulose separator.The zincophilic–NH_(2) and–NH–groups introduced by polyethyleneimine promote Zn^(2+)ion desolvation and nucleation processes.Concurrently,the nanocellulose incorporated into macropores not only significantly enhances mechanical properties but also compensates for macroporous defects within the cellulose separator.The optimized separator exhibits ultralow thickness(18μm),ultrahigh modulus(3.2 GPa),large ionic conductivity(19.0 mS cm^(-1)),high Zn^(2+)ion transfer number(0.63),and good biodegradability.Comprehensive experimental measurements and theoretical analysis reveal that the utilization of this separator contributes to significantly suppressed zinc dendrites and improved electrochemical kinetics.The assembled Zn//Zn cell demonstrates exceptional cycling stability(over 1000 h lifespan at10 m A cm^(-2)and 2 mAh cm^(-2)),and the Zn//MnO_(2) and Zn//I_(2) full batteries maintain excellent longterm cyclability under high cathode mass loadings.This work advances our understanding of multifunctional separator design for next-generation electrochemical energy storage systems.
基金supported by the National Natural Science Foundation of China(32302258,32172317)the Science and Technology Innovation Program of Hunan Province(2024RC3185)+1 种基金Hunan Provincial Natural Science Foundation of China(2023JJ40317)Changsha Municipal Natural Science Foundation(kq2202223).
文摘This study investigated the suppressive effects of Armoracia rusticana(AR)and its three main glucosinolates on both free and bound heterocyclic amines(HAs),along with their mechanisms of free radical quenching using density functional theory.Fish patties were supplemented with varying concentrations of AR(0.5%‒1.5%)and glucosinolates(0.005%‒0.015%),showing a dose-dependent inhibition of HAs and concurrent elimination of free radicals and HAs intermediates.Glucobrassicin demonstrated the highest reactivity,which was verified by frontier orbit analysis and conceptual density functional parameters,consistent with experimental findings.Furthermore,the O-H bond connected to the sulfur atom of glucobrassicin possessed the smallest bond dissociation enthalpy(BDE)value,which indicated that this particular hydrogen atom is most susceptible to react with free radicals.Overall,AR and its glucosinolates,especially glucobrassicin,show promise as natural additives for improving food safety and quality.
基金Supported by The Central Public-Interest Scientific Institution Basal Research Fund,CAFS(2025XT0902)Earmarked for China Agriculture Research System(CARS-46).
文摘The widespread use of herbicides such as glyphosate isopropyl amine salt(GIS)and atrazine(ATZ)poses significant risks to aquatic ecosystems.This study investigated the single and joint acute toxicity of a 1:1 GIS-ATZ mixture on zebrafish(Danio rerio).Acute tests determined 96-h LC_(50) values of 123.41 mg/L for GIS and 103.95 mg/L for ATZ.In the joint toxicity test,these values decreased to 60.96 and 50.88 mg/L,respectively.The Additive Index(AI)analysis revealed a consistent synergistic interaction between the herbicides at all exposure intervals.These findings underscore the enhanced ecological threat of herbicide mixtures and highlight the necessity of considering joint effects in environmental risk assessments.
基金supported by the Key Research and Development Task Project of Xinjiang Uygur Autonomous Region(No.2022B02033)the National Natural Science Foundation of China(Nos.42211530566 and 42311530066)+2 种基金the NSFC-FNRS Joint Program BIOAGRIFILM(No.FNRS PINT-BILATM 2022)the Science and Technology Project of Bijie Tobacco Company of Guizhou Province(No.2022520500240192)the Agricultural Science and Technology Innovation Program(ASTIP)。
文摘The application of poly(butylene adipate-co-terephthalate)(PBAT)biodegradable plastics has long been constrained by insufficient light aging resistance.Hindered amine light stabilizers(HALSs),known as eco-friendly additives,can scavenge free radicals to enhance polymer durability.However,rough choices have resulted in wastage of resources and environmental pressure.Based on the application of plastic films as the background for use,this study systematically evaluates application effects of five HALSs.The films underwent accelerated aging for various durations and were further investigated by a combination of experiments and molecular simulation.Results showed that all HALSs mitigated PBAT light aging,with Chimassorb-944(UV-944)and Tinuvin-770(UV-770)performing the best for real applications.Quantum chemical calculation results showed that UV-944 had stronger anti migration ability.After 300 h of aging,films with UV-944 and UV-770 retained superior tensile strength and elongation at break in the transverse direction compared to neat PBAT films.Polymeric HALSs provided better long-term stability than small-molecule ones.Further spectra analysis indicated that stronger C―O bonds in HALS/PBAT composites correlated with improved photostability.This study offers valuable insights into improving weather resistance of PBAT biodegradable films and optimizing the real application of HALSs.
基金This research was supported by the National Natural Science Foundation of China （Nos. 21672199 and 21790333） and CAS Interdisciplinary Innovation Team.
文摘A new palladium-catalyzed selective aminomethylation of conjugated 1,3-dienes with aminais via double C-N bond activation is described. This simple method provides an effective and rapid approach for the synthesis of linear a,13-unsaturated allylic amines with perfect regioselectivity. Mechanistic studies disclosed that one palladium catalyst cleaved two distinct C-N bond to furnish a cascade double C-N bond activation, in which an allylic 1,3-diamine and allylic 1,2-diamine were initially formed as key intermediates through the palladium-catalyzed C-N bond activation of aminal and the α,β-unsaturated allylic amine was subsequently produced via palladium-catalyzed C-N bond activation of the allylic diamines.
基金ProjectsupportedbytheMajorStateBasicResearchDevelopmentProgram (No .G2 0 0 0 0 775 0 2 )andtheNationalNaturalScienceFoundationofChina (No .2 9732 0 5 0 )
文摘The stereoselective synthesis of O-maltosides by reacting benzoyl-substituted heterocyclic ketene aminals 1 or 2 with acetylated maltosyl bromide 3 was investigated. Compounds 1 or 2 reacted with 3 in the presence of mercuric cyanide to give O-maltosides 4 or 5 with E-configuration. While 1 reacted with 3 in the presence of calcium hydride to give O-maltosides 6 with Z-configuration.
基金support for this work by Hebei Education Department(No.JZX2024004)Central Guidance on Local Science and Technology Development Fund of Hebei Province(No.236Z1404G)+3 种基金the National Natural Science Foundation of China(Nos.22301060 and 21272053)China Postdoctoral Science Foundation(No.2023M730914)the Natural Science Foundation of Hebei Province(Biopharmaceutical Joint Fund No.B2022206008)Project of Science and Technology Department of Hebei Province(No.22567622H)。
文摘Heterogeneous metal-catalyzed chemical conversions with a recyclable catalyst are very ideal and challenging for sustainable organic synthesis.A new bipyridyl-Mo(IV)-carbon nitride(CN-K/Mo-Bpy)was prepared by supporting molybdenum complex on C_(3)N_(4)-K and characterized by FT-IR,XRD,SEM,XPS and ICP-OES.Heterogeneous CN–Mo-Bpy catalyst can be applied to the direct amination of nitroarenes and arylboronic acid,thus constructing various valuable diarylamines in high to excellent yields with a wide substrate scope and good functional group tolerance.It is worth noting that this heterogeneous catalyst has high chemical stability and can be recycled for at least five times without reducing its activity.
基金supported by the Natural Science Foundation of Guangdong Province(2022A1515012158)the National Science Foundation of China(41977138)+3 种基金the Construction Project of Teaching Quality and Teaching Reform in Guangdong Province(SJD202001)the General University Project of Guangdong Provincial Department of Education(2021KCXTD070 and 2021ZDZX4072)the Key Project of Social Welfare and Basic Research of Zhongshan City(2020B2010)the Start-up Fund from the Zhongshan Institute at the University of Electronic Science and Technology in China(419YKQN12)。
文摘In-depth knowledge of the microbes responsible for biogenic amine(BA)production during soy sauce fermentation remains limited.Herein,the variations in the BA profiles,microbial communities,and microbes involved in BA production during the fermentation of soy sauce through Japanese-type(JP)and Cantonese-type(CP)processes were compared.BA analysis revealed that the most abundant BA species were putrescine,tyramine,and histamine in the later three stages(1187.68,785.16,and 193.20 mg/kg on average,respectively).The BA profiles differed significantly,with CP samples containing higher contents of putrescine,tyramine,and histamine(P<0.05)at the end of fermentation.Metagenomic analysis indicated that BA-producing genes exhibited different abundance profiles,with most genes,including spe A,spe B,arg,spe E,and tyr DC,having higher abundances in microbial communities during the CP process.In total,15 high-quality metagenome-assembled genomes(MAGs)were retrieved,of which 10 encoded at BA production-related genes.Enterococcus faecium(MAG10)and Weissella paramesenteroides(MAG5)might be the major tyramine producers.The high putrescine content in CP might be associated with the high abundance of Staphylococcus gallinarum(MAG8).This study provides a comprehensive understanding of the diversity and abundance of genes involved in BA synthesis,especially at the species level,during food fermentation.
基金the NSFC(No.22472112)the Suzhou Foreign Academician Workstation(No.SWY2022001)for financial supportsthe Soochow Municipal Laboratory for Low Carbon Technologies and Industries.
文摘Nitrogenous compounds(i.e.,amines,amides,nitriles,oximes,amino acids and nitrogen-heterocycles derivatives)are important building blocks for synthetic chemistry,pharmaceuticals,and functional materials.Conventional synthetic strategies involve the use of toxic organic nitrogenous precursors or expensive heterogeneous catalysts under elevated temperatures and pressurized oxygen.Heterogeneous electrocatalysis can initiate the activation of inorganic N sources(i.e.,NH_(3)and NO^(-)_(x))under ambient reactions in liquid phase by applying a small bias,thus allowing the synthesis of value?added nitrogenous compounds from carbonyls,alkenes,keto acids,and even carbon dioxide in a sustainable manner without the use of oxidants/reductants.This review outlines recent de-velopments in electrosynthesis of nitrogenous compounds using inorganic N sources,focusing on reaction mechanisms understanding,the design and optimization of efficient electrocatalysts,and the advances in cell configurations for various C‒N coupling reactions.The limitations and challenges in applications are also discussed.
基金supported by the National Natural Science Foundation of China(No.52100133,No.52222005)the Key R&D Program of Yunnan Province(No.202303AC100008)。
文摘Catalyst-aided regeneration is a promising method for reducing the high regeneration energy consumption of amine-based CO_(2)capture technologies.However,the intrinsic relationship between the properties of the acidic sites and their catalytic activity is controversial.In this study,a series of W-based catalysts supported by ZrTiO_(x)were synthesised,and the effects of the intensity,distribution,and type of acid sites were systematically investigated by quantitatively regulating the acidic site properties.The results indicate stronger acidic sites play a more important role in the catalytic reaction.Moreover,the catalysts showed excellent performance only if the Br?nsted acid sites(BASs)and Lewis acid sites(LASs)coexisted.During the catalytic reaction,the BASs facilitated deprotonation,and the LASs promoted the decomposition of carbamates.The ratio of BASs to LASs(B/L)was a critical factor for catalytic activity,wherein optimal performance was achieved when the B/L ratio was close to 1.The 10%HPW/ZrTiO_(x)composite performed better than WO_(3)/ZrTiO_(x)and HSiW/ZrTiO_(x)because it had a stronger acid intensity and a suitable B/L ratio.As a result,the relative heat duty was reduced by 47%compared to 30%aqueous MEA,and the maximum CO_(2)desorption rate was increased by 83%.The Bader charge indicated that the W atoms of HPW/ZrTiO_(x)lost more electrons(0.18)than those of WO_(3)/ZrTiO_(x),which can weaken the O±H bond energy.Consequently,the calculated deprotonation energy is as low as 257 kJ mol^(-1)for HPW/ZrTiO_(x).
文摘Isothiocyanates(ITCs)are an important class of organic compounds characterized by the functional group R-N=C=S.These functional groups are widely found in multiple natural products and pharmaceutical important drugs.Moreover,due to their high and versatile reactivity,they are widely used as an intermediate in organic synthesis.Keeping in view ITCs importance,this review summarizes their synthesis from nitrogen rich raw materials like amines,isocyanides,azides and some other compounds like oximes.Besides their synthesis,their application in organic compound synthesis as an intermediate will also be covered.Future research will likely focus on optimizing the synthesis of multifunctional isothiocyanates,understanding their complex biological mechanisms,exploring new applications,and highlighting the continued importance of isothiocyanates in modern chemistry and biotechnology.
