We prepared the Fe3O4/g‐C3N4nanoparticles(NPs)through a simple electrostatic self‐assembly method with a3:97weight ratio to investigate their Fenton,photo‐Fenton and oxidative functionalities besides photocatalytic...We prepared the Fe3O4/g‐C3N4nanoparticles(NPs)through a simple electrostatic self‐assembly method with a3:97weight ratio to investigate their Fenton,photo‐Fenton and oxidative functionalities besides photocatalytic functionality.We observed an improvement of the Fenton and photo‐Fenton activities of the Fe3O4/g‐C3N4nanocomposites.This improvement was attributed to efficient charge transfer between Fe3O4and g‐C3N4at the heterojunctions,inhibition of electron‐hole recombination,a high surface area,and stabilization of Fe3O4against leaching by the hydrophobic g‐C3N4.The obtained NPs showed a higher degradation potential for rhodamine B(RhB)dye than those of Fe3O4and g‐C3N4.As compared to photocatalysis,the efficiency of RhB degradation in the Fenton and photo‐Fenton reactions was increased by20%and90%,respectively.Additionally,the horseradish peroxidase(HRP)activity of the prepared nanomaterials was studied with3,3,5,5‐tetramethylbenzidinedihydrochloride(TMB)as a substrate.Dopamine oxidation was also examined.Results indicate that Fe3O4/g‐C3N4nanocomposites offers more efficient degradation of RhB dye in a photo‐Fenton system compared with regular photocatalytic degradation,which requires a long time.Our study also confirmed that Fe3O4/g‐C3N4nanocomposites can be used as a potential material for mimicking HRP owing to its high affinity for TMB.These findings suggest good potential for applications in biosensing and as a catalyst in oxidation reactions.展开更多
Breakage of the C-N bond is a structure sensitive process,and the catalyst size significantly affects its activity.On the active metal nanoparticle scale,the role of catalyst size in C-N bond cleavage has not been cle...Breakage of the C-N bond is a structure sensitive process,and the catalyst size significantly affects its activity.On the active metal nanoparticle scale,the role of catalyst size in C-N bond cleavage has not been clearly elucidated.So,Ru catalysts with variable nanoparticle sizes were obtained by modulating the reduction temperature,and the catalytic activity was evaluated using 1,2,3,4-tetrahydroquinoline and o-propylaniline with different C-N bond hybridization patterns as reactants.Results showed a 13 times higher reaction rate for sp3-hybridized C-N bond cleavage than sp2-hybridized C-N bond cleavage,while the reaction rate tended to increase first and then decrease as the catalyst nanoparticle size increased.Different concentrations of terrace,step,and corner sites were found in different sizes of Ru nanoparticles.The relationship between catalytic site variation and C-N bond cleavage activity was further investigated by calculating the turnover frequency values for each site.This analysis indicates that the variation of different sites on the catalyst is the intrinsic factor of the size dependence of C-N bond cleavage activity,and the step atoms are the active sites for the C-N bond cleavage.When Ru nanoparticles are smaller than 1.9 nm,they have a strong adsorption effect on the reactants,which will affect the catalytic performance of the Ru catalyst.Furthermore,these findings were also confirmed on other metallic Pd/Pt catalysts.The role of step sites in C-N bond cleavage was proposed using the density function theory calculations.The reactants have stronger adsorption energies on the step atoms,and step atoms have d-band center nearer to the Fermi level.In this case,the interaction with the reactant is stronger,which is beneficial for activating the C-N bond of the reactant.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 neutron induced reactions on stable Carbon,Nitrogen,and Oxygen isotopes are investigated by using the Talysl.4 toolkit with the default parameters.The neutron incident energy covers a range from 0.20 MeV to85.00 M...The neutron induced reactions on stable Carbon,Nitrogen,and Oxygen isotopes are investigated by using the Talysl.4 toolkit with the default parameters.The neutron incident energy covers a range from 0.20 MeV to85.00 MeV.For^(l2)C and^(14)N,the Talysl.4 results agree with the experimental data,while the parameters should be adjusted for^(l6)O.Some E?windows are found by comparing the main channels of n+C/N/O reactions,which induce element change.In these E_n windows,a specific element is activated to a different one while leaving the other element atoms unchanged.The results will facilitate the research of doping effects in organic materials by using neutron activation technique.展开更多
Herein, we report that a series of novel palladium（II）-NHC complexes （NHC=N-heterocyclic carbene） were synthesized. The structures of all novel complexes were characterized by ^1H NMR, ^13C NMR, FT-IR spectroscopy...Herein, we report that a series of novel palladium（II）-NHC complexes （NHC=N-heterocyclic carbene） were synthesized. The structures of all novel complexes were characterized by ^1H NMR, ^13C NMR, FT-IR spectroscopy and elemental analysis techniques. These palladium（ll）-NHC complexes were tested as efficient catalysts in the direct C-H bond activation of benzoxazole and benzothiazole with aryl bromides in the presence of 1 mol% catalyst loading at 150 ℃ for 4 h. Under the given conditions, various aryl bromides were successfully applied as the arylating reagents to achieve the 2-arylbenzoxazoles and 2-arylbenzothiazoles in acceptable to high yields.展开更多
An interesting and recyclable activated carbon/water catalytic system for efficient synthesis of pyrrolo[1,2-a]quinoxaline derivatives was developed. The intramolecular C-N and C-C bond can be easily constructed in wa...An interesting and recyclable activated carbon/water catalytic system for efficient synthesis of pyrrolo[1,2-a]quinoxaline derivatives was developed. The intramolecular C-N and C-C bond can be easily constructed in water under mild condition. This reaction features a broad substrate scope, a good tolerance to water and air, metal-free, additive-free and redox reagent-free.展开更多
N-Acylpyrrole-type amides are a class of versatile building blocks in asymmetric synthesis.We report that by employing Ni(COD)2/2,2′-bipyridine(5 mol%)catalytic system,the direct,catalytic alcoholysis of N-acylpyrrol...N-Acylpyrrole-type amides are a class of versatile building blocks in asymmetric synthesis.We report that by employing Ni(COD)2/2,2′-bipyridine(5 mol%)catalytic system,the direct,catalytic alcoholysis of N-acylpyrrole-type aromatic and aliphatic amides with both primary and secondary alcohols can be achieved efficiently under very mild conditions(rt,1 h)even at gram scale.By increasing the catalyst loading to 10 mol%,prolonging reaction time(18 h),and/or elevating reaction temperature to 50°C/80°C,the reaction could be extended to both complex and hindered N-acylpyrroles as well as to N-acylpyrazoles,Nacylindoles,and to other(functionalized)primary and secondary alcohols.In all cases,only 1.5 equiv.of alcohol were used.The value of the method has been demonstrated by the racemization-free,catalytic alcoholysis of chiral amides yielded from other asymmetric methodologies.展开更多
In this communication,we disclose the first example of metal-free and site-selective radical fluorination of readily available tertiary alkyl ethers,enabled by synergistic photocatalysis and organocatalysis.This catal...In this communication,we disclose the first example of metal-free and site-selective radical fluorination of readily available tertiary alkyl ethers,enabled by synergistic photocatalysis and organocatalysis.This catalytic combination allows for exclusive fluorination of tertiary C–O bonds under mild conditions even in the presence of competing reaction sites.The excellent functional group tolerance affords valuable access to sterically hindered alkyl fluorides through late-stage modification of complex molecules.The successful use of tertiary alkyl ethers in radical fluorination enhances the structural diversity of aliphatic fluorides that can be derived from naturally abundant alcohols.展开更多
针对测地线活动轮廓(geodesic active contour,GAC)模型轮廓演化速度慢的问题,构造一个区域灰度相似性信息项,对GAC模型的能量泛函进行改进,加快轮廓演化速度,将其用于肺部薄扫CT(computed tomography)图像序列中肺实质的自动分割。采...针对测地线活动轮廓(geodesic active contour,GAC)模型轮廓演化速度慢的问题,构造一个区域灰度相似性信息项,对GAC模型的能量泛函进行改进,加快轮廓演化速度,将其用于肺部薄扫CT(computed tomography)图像序列中肺实质的自动分割。采用基于Nystrom逼近的谱聚类算法分割CT图像序列中间位置CT中的肺实质,计算其灰度均值与标准差,构造区域灰度相似性信息项,以分割好的肺实质轮廓作为初始轮廓,分别从上下两个方向采用改进了能量泛函的GAC模型实现其它切片中肺实质的分割。实验结果表明,该方法能够较好实现肺实质的自动分割,与医师分割结果的重合率可达94.83%,时间消耗较少。展开更多
基金supported by the National Natural Science Foundation of China(51572253,21771171)Scientific Research Grant of Hefei Science Center of CAS(2015SRG-HSC048)+1 种基金cooperation between NSFC and Netherlands Organization for Scientific Research(51561135011)CAS-TWAS Scholarship Program~~
文摘We prepared the Fe3O4/g‐C3N4nanoparticles(NPs)through a simple electrostatic self‐assembly method with a3:97weight ratio to investigate their Fenton,photo‐Fenton and oxidative functionalities besides photocatalytic functionality.We observed an improvement of the Fenton and photo‐Fenton activities of the Fe3O4/g‐C3N4nanocomposites.This improvement was attributed to efficient charge transfer between Fe3O4and g‐C3N4at the heterojunctions,inhibition of electron‐hole recombination,a high surface area,and stabilization of Fe3O4against leaching by the hydrophobic g‐C3N4.The obtained NPs showed a higher degradation potential for rhodamine B(RhB)dye than those of Fe3O4and g‐C3N4.As compared to photocatalysis,the efficiency of RhB degradation in the Fenton and photo‐Fenton reactions was increased by20%and90%,respectively.Additionally,the horseradish peroxidase(HRP)activity of the prepared nanomaterials was studied with3,3,5,5‐tetramethylbenzidinedihydrochloride(TMB)as a substrate.Dopamine oxidation was also examined.Results indicate that Fe3O4/g‐C3N4nanocomposites offers more efficient degradation of RhB dye in a photo‐Fenton system compared with regular photocatalytic degradation,which requires a long time.Our study also confirmed that Fe3O4/g‐C3N4nanocomposites can be used as a potential material for mimicking HRP owing to its high affinity for TMB.These findings suggest good potential for applications in biosensing and as a catalyst in oxidation reactions.
基金supported by the Key Project of National Natural Science Foundation of China(Grant No.22038008)the Science and Technology Innovation Project of National Energy Group China Shenhua Coal to Oil Chemical Co.(Grant No.MZYHG-2021-01).
文摘Breakage of the C-N bond is a structure sensitive process,and the catalyst size significantly affects its activity.On the active metal nanoparticle scale,the role of catalyst size in C-N bond cleavage has not been clearly elucidated.So,Ru catalysts with variable nanoparticle sizes were obtained by modulating the reduction temperature,and the catalytic activity was evaluated using 1,2,3,4-tetrahydroquinoline and o-propylaniline with different C-N bond hybridization patterns as reactants.Results showed a 13 times higher reaction rate for sp3-hybridized C-N bond cleavage than sp2-hybridized C-N bond cleavage,while the reaction rate tended to increase first and then decrease as the catalyst nanoparticle size increased.Different concentrations of terrace,step,and corner sites were found in different sizes of Ru nanoparticles.The relationship between catalytic site variation and C-N bond cleavage activity was further investigated by calculating the turnover frequency values for each site.This analysis indicates that the variation of different sites on the catalyst is the intrinsic factor of the size dependence of C-N bond cleavage activity,and the step atoms are the active sites for the C-N bond cleavage.When Ru nanoparticles are smaller than 1.9 nm,they have a strong adsorption effect on the reactants,which will affect the catalytic performance of the Ru catalyst.Furthermore,these findings were also confirmed on other metallic Pd/Pt catalysts.The role of step sites in C-N bond cleavage was proposed using the density function theory calculations.The reactants have stronger adsorption energies on the step atoms,and step atoms have d-band center nearer to the Fermi level.In this case,the interaction with the reactant is stronger,which is beneficial for activating the C-N bond of the reactant.
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Supported by the National Natural Science Foundation of China(No.11305239)the Program for Science and Technology Innovation Talentsin Universities of Henan Province(13HASTIT046)
文摘The neutron induced reactions on stable Carbon,Nitrogen,and Oxygen isotopes are investigated by using the Talysl.4 toolkit with the default parameters.The neutron incident energy covers a range from 0.20 MeV to85.00 MeV.For^(l2)C and^(14)N,the Talysl.4 results agree with the experimental data,while the parameters should be adjusted for^(l6)O.Some E?windows are found by comparing the main channels of n+C/N/O reactions,which induce element change.In these E_n windows,a specific element is activated to a different one while leaving the other element atoms unchanged.The results will facilitate the research of doping effects in organic materials by using neutron activation technique.
文摘Herein, we report that a series of novel palladium（II）-NHC complexes （NHC=N-heterocyclic carbene） were synthesized. The structures of all novel complexes were characterized by ^1H NMR, ^13C NMR, FT-IR spectroscopy and elemental analysis techniques. These palladium（ll）-NHC complexes were tested as efficient catalysts in the direct C-H bond activation of benzoxazole and benzothiazole with aryl bromides in the presence of 1 mol% catalyst loading at 150 ℃ for 4 h. Under the given conditions, various aryl bromides were successfully applied as the arylating reagents to achieve the 2-arylbenzoxazoles and 2-arylbenzothiazoles in acceptable to high yields.
基金the financial support from the National Natural Science Foundation of China (Nos. 21432009, 21672200, 21472177, 21772185 and 21801233)for the assistance of the product characterization from the Chemistry Experiment Teaching Center of University of Science and Technology of Chinasupported by the Strategic Priority Research Program of the Chinese Academy of Sciences (No. XDB20000000)
文摘An interesting and recyclable activated carbon/water catalytic system for efficient synthesis of pyrrolo[1,2-a]quinoxaline derivatives was developed. The intramolecular C-N and C-C bond can be easily constructed in water under mild condition. This reaction features a broad substrate scope, a good tolerance to water and air, metal-free, additive-free and redox reagent-free.
基金supported by the National Natural Science Foundation of China(21931010)the National Key Research and Development Program of China(2017YFA0207302)the Program for Changjiang Scholars and Innovative Research Team in University of the Ministry of Education,China.
文摘N-Acylpyrrole-type amides are a class of versatile building blocks in asymmetric synthesis.We report that by employing Ni(COD)2/2,2′-bipyridine(5 mol%)catalytic system,the direct,catalytic alcoholysis of N-acylpyrrole-type aromatic and aliphatic amides with both primary and secondary alcohols can be achieved efficiently under very mild conditions(rt,1 h)even at gram scale.By increasing the catalyst loading to 10 mol%,prolonging reaction time(18 h),and/or elevating reaction temperature to 50°C/80°C,the reaction could be extended to both complex and hindered N-acylpyrroles as well as to N-acylpyrazoles,Nacylindoles,and to other(functionalized)primary and secondary alcohols.In all cases,only 1.5 equiv.of alcohol were used.The value of the method has been demonstrated by the racemization-free,catalytic alcoholysis of chiral amides yielded from other asymmetric methodologies.
基金supported by the National Natural Science Foundation of China(21971108,21702098)the Natural Science Foundation of Jiangsu Province(BK20190006)+4 种基金Fundamental Research Funds for the Central Universities(020514380176)“Jiangsu Six Peak Talent Project”“1000-Youth Talents Plan’’start-up funds from Nanjing Universitysupported by the Scientific Research Foundation of Graduate School of Nanjing University(2018CL05)
文摘In this communication,we disclose the first example of metal-free and site-selective radical fluorination of readily available tertiary alkyl ethers,enabled by synergistic photocatalysis and organocatalysis.This catalytic combination allows for exclusive fluorination of tertiary C–O bonds under mild conditions even in the presence of competing reaction sites.The excellent functional group tolerance affords valuable access to sterically hindered alkyl fluorides through late-stage modification of complex molecules.The successful use of tertiary alkyl ethers in radical fluorination enhances the structural diversity of aliphatic fluorides that can be derived from naturally abundant alcohols.
文摘针对测地线活动轮廓(geodesic active contour,GAC)模型轮廓演化速度慢的问题,构造一个区域灰度相似性信息项,对GAC模型的能量泛函进行改进,加快轮廓演化速度,将其用于肺部薄扫CT(computed tomography)图像序列中肺实质的自动分割。采用基于Nystrom逼近的谱聚类算法分割CT图像序列中间位置CT中的肺实质,计算其灰度均值与标准差,构造区域灰度相似性信息项,以分割好的肺实质轮廓作为初始轮廓,分别从上下两个方向采用改进了能量泛函的GAC模型实现其它切片中肺实质的分割。实验结果表明,该方法能够较好实现肺实质的自动分割,与医师分割结果的重合率可达94.83%,时间消耗较少。
