建立了一种在温和条件下,用可见光催化合成一系列3,4-二氢异喹啉-1(2H)-酮及其衍生物的方法。该方法在室温条件下,以2-烯丙基-N-甲氧基苯甲酰胺为模板底物,以碘化钾作为光催化剂,25 W 460 nm的蓝色LED灯照射下,合成一系列3,4-二氢异喹啉...建立了一种在温和条件下,用可见光催化合成一系列3,4-二氢异喹啉-1(2H)-酮及其衍生物的方法。该方法在室温条件下,以2-烯丙基-N-甲氧基苯甲酰胺为模板底物,以碘化钾作为光催化剂,25 W 460 nm的蓝色LED灯照射下,合成一系列3,4-二氢异喹啉-1(2H)-酮衍生物,最高产率可达到83%。该合成路径具有底物适用范围广、经济实用等特点,为3,4-二氢异喹啉-1(2H)-酮衍生物合成提供了一种经济简便的方法。展开更多
有机化学是化学专业、药学专业的一门重要专业课,它的教学内容复杂,知识点多,传统的教学方式教学效果不佳,因此成为教学改革的一个重要方向。在有机化学教学中运用成果导向教育(outcome based education, OBE)理念,同时在教学内容、教...有机化学是化学专业、药学专业的一门重要专业课,它的教学内容复杂,知识点多,传统的教学方式教学效果不佳,因此成为教学改革的一个重要方向。在有机化学教学中运用成果导向教育(outcome based education, OBE)理念,同时在教学内容、教学模式和知识拓展上对传统的有机化学教学模式进行改革,可以使学生对有机化学产生浓厚的兴趣。对此,文章从有机化学课程教学目标着手,重点阐述了基于OBE理念的有机化学教学策略,旨在使学生的整体素质得到全面提高。展开更多
Dual atomic catalysts(DAC),particularly copper(Cu_(2))-based nitrogen(N)doped graphene,show great potential to effectively convert CO_(2)and nitrate(NO_(3)-)into important industrial chemicals such as ethylene,glycol,...Dual atomic catalysts(DAC),particularly copper(Cu_(2))-based nitrogen(N)doped graphene,show great potential to effectively convert CO_(2)and nitrate(NO_(3)-)into important industrial chemicals such as ethylene,glycol,acetamide,and urea through an efficient catalytical process that involves C–C and C–N coupling.However,the origin of the coupling activity remained unclear,which substantially hinders the rational design of Cu-based catalysts for the N-integrated CO_(2)reduction reaction(CO_(2)RR).To address this challenge,this work performed advanced density functional theory calculations incorporating explicit solvation based on a Cu_(2)-based N-doped carbon(Cu_(2)N_(6)C_(10))catalyst for CO_(2)RR.These calculations are aimed to gain insight into the reaction mechanisms for the synthesis of ethylene,acetamide,and urea via coupling in the interfacial reaction micro-environment.Due to the sluggishness of CO_(2),the formation of a solvation electric layer by anions(F^(-),Cl^(-),Br^(-),and I^(-))and cations(Na+,Mg^(2+),K+,and Ca^(2+))leads to electron transfer towards the Cu surface.This process significantly accelerates the reduction of CO_(2).These results reveal that*CO intermediates play a pivotal role in N-integrated CO_(2)RR.Remarkably,the Cu_(2)-based N-doped carbon catalyst examined in this study has demonstrated the most potential for C–N coupling to date.Our findings reveal that through the process of a condensation reaction between*CO and NH_(2)OH for urea synthesis,*NO_(3)-is reduced to*NH_(3),and*CO_(2)to*CCO at dual Cu atom sites.This dual-site reduction facilitates the synthesis of acetamide through a nucleophilic reaction between NH_(3)and the ketene intermediate.Furthermore,we found that the I-and Mg^(2+)ions,influenced by pH,were highly effective for acetamide and ammonia synthesis,except when F-and Ca^(2+)were present.Furthermore,the mechanisms of C–N bond formation were investigated via ab-initio molecular dynamics simulations,and we found that adjusting the micro-environment can change the dominant side reaction,shifting from hydrogen production in acidic conditions to water reduction in alkaline ones.This study introduces a novel approach using ion-H_(2)O cages to significantly enhance the efficiency of C–N coupling reactions.展开更多
Biomass conversion offers an efficient approach to alleviate the energy and environmental issues.Electrochemical oxidation of 5-hydroxymethylfurfural(HMF)has attracted tremendous attention in the latest few years for ...Biomass conversion offers an efficient approach to alleviate the energy and environmental issues.Electrochemical oxidation of 5-hydroxymethylfurfural(HMF)has attracted tremendous attention in the latest few years for the mild synthesis conditions and high conversion efficiency to obtain 2,5-furan dicarboxylic acid(FDCA),but there still remain problems such as limited yield,short cycle life,and ambiguous reaction mechanism.Despite many reviews highlighting a variety of electrocatalysts for electrochemical oxidation of HMF,a detailed discussion of the structural modulation of catalyst and the underlying catalytic mechanism is still lacking.We herein provide a comprehensive summary of the recent development of electrochemical oxidation of HMF to FDCA,particularly focusing on the mechanism studies as well as the advanced strategies developed to regulate the structure and optimize the performance of the electrocatalysts,including heterointerface construction,defect engineering,single-atom engineering,and in situ reconstruction.Experimental characterization techniques and theoretical calculation methods for mechanism and active site studies are elaborated,and challenges and future directions of electrochemical oxidation of HMF are also prospected.This review will provide guidance for designing advanced catalysts and deepening the understanding of the reaction mechanism beneath electrochemical oxidation of HMF to FDCA.展开更多
Photocatalytic oxygen reduction for hydrogen peroxide(H_(2)O_(2))synthesis presents a green and costeffective production method.However,achieving highly selective H_(2)O_(2)synthesis remains challenging,necessitating ...Photocatalytic oxygen reduction for hydrogen peroxide(H_(2)O_(2))synthesis presents a green and costeffective production method.However,achieving highly selective H_(2)O_(2)synthesis remains challenging,necessitating precise control over free radical reaction pathways and minimizing undesirable oxidative by-products.Herein,we report for the visible light-driven simultaneous co-photocatalytic reduction of O2to H_(2)O_(2)and oxidation of biomass using the atomic rubidium-nitride modified carbon nitride(CNRb).The optimized CNRb catalyst demonstrates a record photoreduction rate of 8.01 mM h^(-1)for H_(2)O_(2)generation and photooxidation rate of 3.75 mM h^(-1)for furfuryl alcohol to furoic acid,achieving a remarkable solar-to-chemical conversion(SCC)efficiency of up to 2.27%.Experimental characterizations and DFT calculation disclosed that the introducing atomic Rb–N configurations allows for the high-selective generation of superoxide radicals while suppressing hydroxyl free radical formation.This is because the Rb–N serves as the new alternative site to perceive a stronger connection position for O2adsorption and reinforce the capability to extract protons,thereby triggering a high selective redox product formation.This study holds great potential in precisely regulating reactive radical processes at the atomic level,thereby paving the way for efficient synthesis of H_(2)O_(2)coupled with biomass valorization.展开更多
The defense mechanisms induced in wild Chinese pine(Pinus tabuliformis)in response to herbivores are not well characterized,especially in the field.To address this knowledge gap,we established a biological model syste...The defense mechanisms induced in wild Chinese pine(Pinus tabuliformis)in response to herbivores are not well characterized,especially in the field.To address this knowledge gap,we established a biological model system to evaluate proteome variations in pine needles after feeding by the Chinese pine caterpillar(Dendrolimus tabulaeformis),a major natural enemy and dominant herbivore.Quantitative tandem mass tag(TMT)proteomics and bioinformatics were utilized to systematically identify differentially abundant proteins implicated in the induced defense response of Chinese pine.We validated key protein changes using parallel reaction monitoring(PRM)technology.Pathway analysis revealed that the induced defenses involved phenylpropanoid,coumarin,and flavonoid biosynthesis,among other processes.To elucidate the regulatory patterns underlying pine resistance,we determined the activities of defense enzymes and levels of physiological and biochemical compounds.In addition,the expression of upstream genes for key proteins was validated by qRT-PCR.Our results provide new molecular insights into the induced defense mechanisms in Chinese pine against this caterpillar in the field.A better understanding of these defense strategies will inform efforts to breed more-resistant pine varieties.展开更多
文摘建立了一种在温和条件下,用可见光催化合成一系列3,4-二氢异喹啉-1(2H)-酮及其衍生物的方法。该方法在室温条件下,以2-烯丙基-N-甲氧基苯甲酰胺为模板底物,以碘化钾作为光催化剂,25 W 460 nm的蓝色LED灯照射下,合成一系列3,4-二氢异喹啉-1(2H)-酮衍生物,最高产率可达到83%。该合成路径具有底物适用范围广、经济实用等特点,为3,4-二氢异喹啉-1(2H)-酮衍生物合成提供了一种经济简便的方法。
文摘有机化学是化学专业、药学专业的一门重要专业课,它的教学内容复杂,知识点多,传统的教学方式教学效果不佳,因此成为教学改革的一个重要方向。在有机化学教学中运用成果导向教育(outcome based education, OBE)理念,同时在教学内容、教学模式和知识拓展上对传统的有机化学教学模式进行改革,可以使学生对有机化学产生浓厚的兴趣。对此,文章从有机化学课程教学目标着手,重点阐述了基于OBE理念的有机化学教学策略,旨在使学生的整体素质得到全面提高。
基金National Natural Science Foundation of China(U22B20149,22308376)Outstanding Young Scholars Foundation of China University of Petroleum(Beijing)(2462023BJRC015)Foundation of United Institute for Carbon Neutrality(CNIF20230209)。
文摘Dual atomic catalysts(DAC),particularly copper(Cu_(2))-based nitrogen(N)doped graphene,show great potential to effectively convert CO_(2)and nitrate(NO_(3)-)into important industrial chemicals such as ethylene,glycol,acetamide,and urea through an efficient catalytical process that involves C–C and C–N coupling.However,the origin of the coupling activity remained unclear,which substantially hinders the rational design of Cu-based catalysts for the N-integrated CO_(2)reduction reaction(CO_(2)RR).To address this challenge,this work performed advanced density functional theory calculations incorporating explicit solvation based on a Cu_(2)-based N-doped carbon(Cu_(2)N_(6)C_(10))catalyst for CO_(2)RR.These calculations are aimed to gain insight into the reaction mechanisms for the synthesis of ethylene,acetamide,and urea via coupling in the interfacial reaction micro-environment.Due to the sluggishness of CO_(2),the formation of a solvation electric layer by anions(F^(-),Cl^(-),Br^(-),and I^(-))and cations(Na+,Mg^(2+),K+,and Ca^(2+))leads to electron transfer towards the Cu surface.This process significantly accelerates the reduction of CO_(2).These results reveal that*CO intermediates play a pivotal role in N-integrated CO_(2)RR.Remarkably,the Cu_(2)-based N-doped carbon catalyst examined in this study has demonstrated the most potential for C–N coupling to date.Our findings reveal that through the process of a condensation reaction between*CO and NH_(2)OH for urea synthesis,*NO_(3)-is reduced to*NH_(3),and*CO_(2)to*CCO at dual Cu atom sites.This dual-site reduction facilitates the synthesis of acetamide through a nucleophilic reaction between NH_(3)and the ketene intermediate.Furthermore,we found that the I-and Mg^(2+)ions,influenced by pH,were highly effective for acetamide and ammonia synthesis,except when F-and Ca^(2+)were present.Furthermore,the mechanisms of C–N bond formation were investigated via ab-initio molecular dynamics simulations,and we found that adjusting the micro-environment can change the dominant side reaction,shifting from hydrogen production in acidic conditions to water reduction in alkaline ones.This study introduces a novel approach using ion-H_(2)O cages to significantly enhance the efficiency of C–N coupling reactions.
基金National Natural Science Foundation of China(22272150,22302177)Major Program of Zhejiang Provincial Natural Science Foundation of China(LD22B030002)+2 种基金Zhejiang Provincial Ten Thousand Talent Program(2021R51009)Public Technology Application Project of Jinhua City(2022-4-067)Self Designed Scientific Research of Zhejiang Normal University(2021ZS0604)。
文摘Biomass conversion offers an efficient approach to alleviate the energy and environmental issues.Electrochemical oxidation of 5-hydroxymethylfurfural(HMF)has attracted tremendous attention in the latest few years for the mild synthesis conditions and high conversion efficiency to obtain 2,5-furan dicarboxylic acid(FDCA),but there still remain problems such as limited yield,short cycle life,and ambiguous reaction mechanism.Despite many reviews highlighting a variety of electrocatalysts for electrochemical oxidation of HMF,a detailed discussion of the structural modulation of catalyst and the underlying catalytic mechanism is still lacking.We herein provide a comprehensive summary of the recent development of electrochemical oxidation of HMF to FDCA,particularly focusing on the mechanism studies as well as the advanced strategies developed to regulate the structure and optimize the performance of the electrocatalysts,including heterointerface construction,defect engineering,single-atom engineering,and in situ reconstruction.Experimental characterization techniques and theoretical calculation methods for mechanism and active site studies are elaborated,and challenges and future directions of electrochemical oxidation of HMF are also prospected.This review will provide guidance for designing advanced catalysts and deepening the understanding of the reaction mechanism beneath electrochemical oxidation of HMF to FDCA.
基金National Natural Science Foundation of China(22309032,22109120,and 62104170)Guangdong Basic and Applied Basic Research Foundation(2022A1515011737)+2 种基金Science and Technology Program of Guangzhou(2023A04J1395)GDAS’Project of Science and Technology Development(2021GDASYL-20210102010)Zhejiang Provincial Natural Science Foundation of China(LY23F040001)。
文摘Photocatalytic oxygen reduction for hydrogen peroxide(H_(2)O_(2))synthesis presents a green and costeffective production method.However,achieving highly selective H_(2)O_(2)synthesis remains challenging,necessitating precise control over free radical reaction pathways and minimizing undesirable oxidative by-products.Herein,we report for the visible light-driven simultaneous co-photocatalytic reduction of O2to H_(2)O_(2)and oxidation of biomass using the atomic rubidium-nitride modified carbon nitride(CNRb).The optimized CNRb catalyst demonstrates a record photoreduction rate of 8.01 mM h^(-1)for H_(2)O_(2)generation and photooxidation rate of 3.75 mM h^(-1)for furfuryl alcohol to furoic acid,achieving a remarkable solar-to-chemical conversion(SCC)efficiency of up to 2.27%.Experimental characterizations and DFT calculation disclosed that the introducing atomic Rb–N configurations allows for the high-selective generation of superoxide radicals while suppressing hydroxyl free radical formation.This is because the Rb–N serves as the new alternative site to perceive a stronger connection position for O2adsorption and reinforce the capability to extract protons,thereby triggering a high selective redox product formation.This study holds great potential in precisely regulating reactive radical processes at the atomic level,thereby paving the way for efficient synthesis of H_(2)O_(2)coupled with biomass valorization.
基金supported by the Science and Technology Development Program of Hebei Agricultural University,the Research on Molecular Mechanisms of Population Differentiation and Adaptation of Forest Pests and Insects under Environmental Stress(grant No.:30771739)Forest Pests and Diseases(grant No.:1528003)the National Natural Science Foundation of China for the study of community regulatory mechanisms of insect pest pandemics in larch plantation forests(Grant No.:32371882).
文摘The defense mechanisms induced in wild Chinese pine(Pinus tabuliformis)in response to herbivores are not well characterized,especially in the field.To address this knowledge gap,we established a biological model system to evaluate proteome variations in pine needles after feeding by the Chinese pine caterpillar(Dendrolimus tabulaeformis),a major natural enemy and dominant herbivore.Quantitative tandem mass tag(TMT)proteomics and bioinformatics were utilized to systematically identify differentially abundant proteins implicated in the induced defense response of Chinese pine.We validated key protein changes using parallel reaction monitoring(PRM)technology.Pathway analysis revealed that the induced defenses involved phenylpropanoid,coumarin,and flavonoid biosynthesis,among other processes.To elucidate the regulatory patterns underlying pine resistance,we determined the activities of defense enzymes and levels of physiological and biochemical compounds.In addition,the expression of upstream genes for key proteins was validated by qRT-PCR.Our results provide new molecular insights into the induced defense mechanisms in Chinese pine against this caterpillar in the field.A better understanding of these defense strategies will inform efforts to breed more-resistant pine varieties.
