During last several years,electron acceptors for organic sol-ar cells(OSCs)have experienced three major innovations.The first invention was a fused-ring electron acceptor(FREA),ITIC,reported by Zhan et al.in 2015,whic...During last several years,electron acceptors for organic sol-ar cells(OSCs)have experienced three major innovations.The first invention was a fused-ring electron acceptor(FREA),ITIC,reported by Zhan et al.in 2015,which consists of an in-dacenodithienothiophene(IDTT)donor core and two 3-dicy-anomethylene-1-indanone(IC)as the end-groups[1].ITIC cells exhibited comparable performance to PC61BM cells,and in-spired the development of hundreds nonfullerene acceptors(NFAs).The second breakthrough is the 14.08%power con-version efficiency(PCE)delivered by a low-bandgap non-fullerene acceptor COi 8DFIC with strong NIR absorption,invented by Ding et al.[2,3].The third star acceptor is Y6,developed by Zou et al.in 2019[4].Y6 and its derivatives(Y-series NFAs)are very promising[5,6].Ding et al.developed polymer donor D18 and its outstanding derivatives[7−10],and the D18:Y6 cells gave a PCE of 18.22%[7],which was the first time for OSCs to deliver PCEs over 18%.展开更多
We use an automated research platform combined with machine learning to assess and understand the resilience against air and light during production of organic photovoltaic(OPV)devices from over 40 donor and acceptor ...We use an automated research platform combined with machine learning to assess and understand the resilience against air and light during production of organic photovoltaic(OPV)devices from over 40 donor and acceptor combina-tions.The standardized protocol and high reproducibility of the platform results in a dataset of high variety and veracity to deploy machine learning models to encounter links between stability and chemical,energetic,and mor-phological structure.We find that the strongest predictor for air/light resilience during production is the effective gap Eg,eff which points to singlet oxygen rather than the superoxide anion being the dominant agent in degradation under processing conditions.A similarly good prediction of air/light resilience can also be achieved by considering only features from chemical structure,that is,information which is available prior to any experimentation.展开更多
Heme responsible for the dioxygen fixation,transport and conversion is a metalloporphyrin complex highly dependent on its diverse geometry of ligand.In this work,a trans-ortho-di-strapped zinc porphyrin with dome-like...Heme responsible for the dioxygen fixation,transport and conversion is a metalloporphyrin complex highly dependent on its diverse geometry of ligand.In this work,a trans-ortho-di-strapped zinc porphyrin with dome-like deformation was synthesized by thermodynamically controlling the formation of transprecursor of porphyrinogen.Its single-crystal structure demonstrated that the asymmetric treatment of porphyrin achieves three goals of creating two secondary coordination sphere(SCS)bulks,maintaining a unique dome deformation,and making atomic out-of-plane deviation.In this way,this metallic complex integrates at least three key features of the pocket structure,the differentiated axial ligations,and the ring distortion,making it an ideal heme analog.展开更多
Organisms are capable of self-growth through the integration of the nutrients provided by the external environment.This process slows down when they grow.In this study,we mimicked this self-regulated growth via a simp...Organisms are capable of self-growth through the integration of the nutrients provided by the external environment.This process slows down when they grow.In this study,we mimicked this self-regulated growth via a simple swelling-polymerization strategy in which the stretching polymer chains in the original networks provide entropic elasticity to restrict growth in high growth cycles.Using typical covalently crosslinked polymers,such as acrylamide-based hydrogels and HBA-based elastomers,as examples,we demonstrate that the crosslinked polymers can absorb polymerizable compounds through a swelling-polymerization process to expand their sizes,but the growth extent becomes smaller with increasing growth cycle until reaching a plateau.In addition to their size,these materials become stiffer and exhibit less swelling ability in solvents.Our work not only provides a new growing mode to tune the properties of crosslinked polymers but also discloses the underlying mechanism of crosslinked polymers in multi-cyclic swelling conditions.展开更多
A new class of axially chiral aryl-alkene-indole frameworks have been designed,and the first catalytic asymmetric construction of such scaffolds has been established by the strategy of organocatalytic(Z/E)-selective a...A new class of axially chiral aryl-alkene-indole frameworks have been designed,and the first catalytic asymmetric construction of such scaffolds has been established by the strategy of organocatalytic(Z/E)-selective and enantioselective(4+3)cyclization of 3-alkynyl-2-indolylmethanols with 2-naphthols or phenols(all>95:5 E/Z,up to 98% yield,97% ee).This reaction also represents the first catalytic asymmetric construction of axially chiral alkene-heteroaryl scaffolds,which will add a new member to the atropisomeric family.This approach has not only confronted the great challenges in constructing axially chiral alkene-heteroaryl scaffolds but also provided a powerful strategy for the enantioselective construction of axially chiral aryl-alkene-indole frameworks.展开更多
Direct,in situ selective detection of intracellular formaldehyde(FA)is of great significance for understanding its function in FA-related diseases.Herein,red carbon dots(RCD)are reported as label-free two-photon fluor...Direct,in situ selective detection of intracellular formaldehyde(FA)is of great significance for understanding its function in FA-related diseases.Herein,red carbon dots(RCD)are reported as label-free two-photon fluorescent nanoprobes for detecting and imaging of FA.Upon addition of FA,the-NH2 groups of RCD could quickly and specially react with aldehydes to form Schiff base and then the strong fluorescence of RCD with blue-shift emission is recovery due to the destruction of the hydrogen bond interaction between RCD and water.In addition,the nanoprobes exhibit outsta nding photo stability,rapid response(<1 min),high sensitivity(~9.9μmol/L)and excellent selectivity toward FA over other aldehyde group compounds.Notably,owing to the good cell-membrane permeability and biocompatibility,as well as the large two-photon absorption cross-section,the as-prepared RCD can be used as label-free nanoprobes for selectively detecting and imaging FA in living cells and zebrafishes through one-photon and two-photon excitation.Moreover,RCD could stain the tissue of zebrafishes at depths interval of up to 240μm under two-photon excitation.This research implied that RCD are promising tools for directly and in situ imaging FA in vivo,thus providing critical insights into FA-related pathophysiological processes.展开更多
Organic solar cells(OSCs)as a promising photovoltaic tech-nology have attracted great attention due to its unique advant-ages,such as solution processing,low cost,lightweight and ex-cellent mechanical flexibility[1−5]...Organic solar cells(OSCs)as a promising photovoltaic tech-nology have attracted great attention due to its unique advant-ages,such as solution processing,low cost,lightweight and ex-cellent mechanical flexibility[1−5].Conventional OSCs always employ fullerene derivatives,e.g.展开更多
The industrial application of nano-photocatalysts in wastewater treatment has been severely restricted for a long time due to their difficult separation,poor reusability,and low efficiency.In this work,a facile strate...The industrial application of nano-photocatalysts in wastewater treatment has been severely restricted for a long time due to their difficult separation,poor reusability,and low efficiency.In this work,a facile strategy was proposed to enhance the photocatalytic activity and recovery performance of Ag@AgCl nanocatalysts.Biological veins(Bio-veins)with a unique 3D porous construction were used as carriers for the in-situ growth of Ag@AgCl nanoparticles.Scanning electron microscopy results showed that the Ag@AgCl nanoparticles were uniformly loaded on the surface and interior of the Bio-veins,and the size of the Ag@AgCl nanoparticles immobilized on the Bio-veins(50–300 nm)was significantly smaller than Ag@AgCl obtained by the co-precipitation method(1–3μm).The Bio-veins played a vital role in the photocatalysis reaction system.The degradation efficiency of the Ag@AgCl/Bio-veins(CI4)was up to 3.50 times as high as pure Ag@AgCl.Furthermore,the composites also exhibited excellent recyclability and stability under both visible and solar light.This work provided a suitable strategy for nano-photocatalysts for practical application and may also offer new possibilities for the high-value utilization of biomass materials.展开更多
The reactivity of the metalloporphyrins was closely related to their ligand effect at axial position. The electronic properties of six model Co（II） porphyrins are investigated by spectral and electrochemical methods...The reactivity of the metalloporphyrins was closely related to their ligand effect at axial position. The electronic properties of six model Co（II） porphyrins are investigated by spectral and electrochemical methods. Structural parameters of the COOI） complexes are directly obtained from their crystal structures. We demonstrate that the unpaired 3d electron of low-spin Co（II） ions in nonplanar Co（II） porphyrin complexes activated by core contraction of porphyrin macrocycles can be further activated by the axial ligation of imidazole. The activated electron can combine with a n orbital of the porphyrin ring to form a new d-π orbital, which can induce the Q-band of Co（II） porphyrins to visibly split. Addition of imidazole causes the Co（II）/Co（III） and Co（II）/Co（I） reactions to shift to more negative potential. Our results indicate that strong axial ligation and core contraction both play important roles in electron transfer in redox catalysis involving Co（II） complexes.展开更多
Single atom catalysts (SACs), exhibiting outstanding properties for a wide variety of chemical reactions, have become the most active new frontier in heterogeneous catalysis[1]. Benefitting from the uniform coordinati...Single atom catalysts (SACs), exhibiting outstanding properties for a wide variety of chemical reactions, have become the most active new frontier in heterogeneous catalysis[1]. Benefitting from the uniform coordination environment, every dispersed single atom in SACs can work as active centers to participate in catalytic cycles, presenting the maximum atom utilization efficiency.展开更多
In this review,the recent development about using DESs as green solvents in transition metal catalyzed organic reactions was highlighted.Firstly,the development of DESs was simply introduced.After presenting the advan...In this review,the recent development about using DESs as green solvents in transition metal catalyzed organic reactions was highlighted.Firstly,the development of DESs was simply introduced.After presenting the advantages of DESs,transition metals catalyzed organic reactions using DESs as green solvents were classified and introduced in detail.Different transition metals such as Au,metal impregnated on magnetite,Pd and Ru catalyzed organic reactions proceeded smoothly in DESs and gave corresponding products in good yields.And in some cases,the catalytic systems could be recycled up to several times without any decrease in activity.展开更多
In this review,the recent development in transition metal catalyzed cross coupling of nitroarenes was highlighted.Firstly,development of transition metal catalyzed cross coupling was simply introduced.After presenting...In this review,the recent development in transition metal catalyzed cross coupling of nitroarenes was highlighted.Firstly,development of transition metal catalyzed cross coupling was simply introduced.After presenting the advantages of nitroarenes,transition metal catalyzed cross coupling using nitroarenes as electrophilic coupling partners was classified and introduced in detail.Based on different chemical bonds such as C–O,C–S,C-C and C–N bonds constructed,different kinds cross coupling of nitroarenes would be highlighted and the plausible reaction mechanism would be presented if available.展开更多
Quinoxaline-3-carboxylates and analogues are prevalent key structural motifs in bioactive natural products and synthetic drugs.However, the practical protocol for preparation of these motifs from simple raw materials ...Quinoxaline-3-carboxylates and analogues are prevalent key structural motifs in bioactive natural products and synthetic drugs.However, the practical protocol for preparation of these motifs from simple raw materials under mild conditions remains rare. In this article, we report a facile protocol for the efficient preparation of various quinoxaline-3-carbonyl compounds(30 examples,63%–92%) through oxidation coupling of quinoxalin-2(1H)-ones with readily available carbazates(or acyl hydrazines) in the presence of K_2S_2O_8 as an oxidant in metal-and base-free conditions. When tert-butyl carbazate was used as the coupling reagent,the decarboxylation product 3-(tert-butyl)-1-methylquinoxalin-2(1H)-one was obtained. The application of this process into a gram-scale synthesis can be easily accomplished. Mechanistic investigations reveal that the functionalization of quinoxalin-2(1H)-ones via a free-radical pathway.展开更多
The clinical approval of platinum-based drugs has prompted the development of novel metallo-complexes during the last several decades,while severe problems,especially for poor water solubility,drug resistance and toxi...The clinical approval of platinum-based drugs has prompted the development of novel metallo-complexes during the last several decades,while severe problems,especially for poor water solubility,drug resistance and toxicity in patients,greatly hindered the clinical trials and curative efficacy.To address these issues,the concept of metallo-prodrugs has been proposed for oncology.Some stimuliactivable metallo-prodrugs provide new insights for designing and preparing site-specific prodrugs with maximized therapeutic efficacy and negligible unfavorable by-effects.In this review,recent progress in stimuli-activable metalloprodrugs in the past 20 years has been overviewed,where endogenous and exogenous stimuli have been involved.Typical examples of smart stimuli-activable metallo-prodrugs are discussed regarding to their molecular structure,activation mechanism,and promising biomedical applications.In the end,challenges and future perspectives in metallo-prodrugs have been discussed.展开更多
The interface defects and nickel vacancies of the NiO_(x)lead to interface charge recombination,which limits its application in perovskite solar cells.Here,graphdiyne oxide(GDYO)was added to NiO_(x)as an inorganic hol...The interface defects and nickel vacancies of the NiO_(x)lead to interface charge recombination,which limits its application in perovskite solar cells.Here,graphdiyne oxide(GDYO)was added to NiO_(x)as an inorganic hole transporting material.It is found that the average carrier lifetime declined from 29.2 ns to 5.4 ns and the recombination resistance increased significantly after the GDYO adding determined by the time-resolved photoluminescence and electrochemical impedance spectroscopy analysis.We further demonstrated that the GDYO adding to NiO_(x)effectively improved the charge extraction,accelerated the charge transportation and suppressed the charge recombination.Consequently,the optimized NiO_(x)(GDYO)-based cell showed superior performance with a higher fill factor(81.99%)and improved stability with respect to the reference device.This method provides a new method for property regulation of NiO_(x)in inverted planar MAPbI_(3) perovskite solar cells.展开更多
基金the National Natural Science Foundation of China(21604021)Hunan Provincial Natural Science Foundation(2018JJ3141)and the Innovation Team of Huxiang High-level Talent Gathering Engineering(2021RC5028)+1 种基金the National Key Research and Development Program of China(2017YFA0206600)the National Natural Science Foundation of China(51773045,21772030,51922032,21961160720)for financial support.
文摘During last several years,electron acceptors for organic sol-ar cells(OSCs)have experienced three major innovations.The first invention was a fused-ring electron acceptor(FREA),ITIC,reported by Zhan et al.in 2015,which consists of an in-dacenodithienothiophene(IDTT)donor core and two 3-dicy-anomethylene-1-indanone(IC)as the end-groups[1].ITIC cells exhibited comparable performance to PC61BM cells,and in-spired the development of hundreds nonfullerene acceptors(NFAs).The second breakthrough is the 14.08%power con-version efficiency(PCE)delivered by a low-bandgap non-fullerene acceptor COi 8DFIC with strong NIR absorption,invented by Ding et al.[2,3].The third star acceptor is Y6,developed by Zou et al.in 2019[4].Y6 and its derivatives(Y-series NFAs)are very promising[5,6].Ding et al.developed polymer donor D18 and its outstanding derivatives[7−10],and the D18:Y6 cells gave a PCE of 18.22%[7],which was the first time for OSCs to deliver PCEs over 18%.
基金The authors want to thank the Deutsche Forschungsge-meinschaft(DFG)for financial support in scope of the DFG INST 90/917-1 FUGGof the projects FKZ BR 4031/21-1 and BR 4031/22-1+6 种基金We also gratefully acknowledge the grants“ELF-PV-Design and development of solution processed functional materials for the next generations of PV technologies”(No.44-6521a/20/4)“Solar Factory of the Future”(FKZ 20.2-3410.5-4-5)by the Bavarian State GovernmentC.J.B.gratefully acknowledges the financial support through the Bavarian Initiative“Solar Technologies go Hybrid”(SolTech)and the SFB 953(DFG,project No.182849149)N.L.and C.J.B.acknowledge the financial support by the DFG research unit project“POPULAR”(FOR 5387,project no.461909888)X.D.thanks Natural Science Foundation of Shandong Province(2022HWYQ-012)N.L.acknowledges the financial support by the National Natural Science Foundation of China(52394273,52373179)L.Ding thanks the National Key Research and Development Program of China(2023YFE0116800)for financial support.
文摘We use an automated research platform combined with machine learning to assess and understand the resilience against air and light during production of organic photovoltaic(OPV)devices from over 40 donor and acceptor combina-tions.The standardized protocol and high reproducibility of the platform results in a dataset of high variety and veracity to deploy machine learning models to encounter links between stability and chemical,energetic,and mor-phological structure.We find that the strongest predictor for air/light resilience during production is the effective gap Eg,eff which points to singlet oxygen rather than the superoxide anion being the dominant agent in degradation under processing conditions.A similarly good prediction of air/light resilience can also be achieved by considering only features from chemical structure,that is,information which is available prior to any experimentation.
基金supported by the Institute of Elemento-organic Chemistry,Nankai University and the Scientific Research Fund of Hunan Provincial Education Department(No.20A195)Hunan Provincial Natural Science Foundation of China(No.2020JJ4292)the Science and Technology innovation Program of Hunan Province(No.2021RC5028).
文摘Heme responsible for the dioxygen fixation,transport and conversion is a metalloporphyrin complex highly dependent on its diverse geometry of ligand.In this work,a trans-ortho-di-strapped zinc porphyrin with dome-like deformation was synthesized by thermodynamically controlling the formation of transprecursor of porphyrinogen.Its single-crystal structure demonstrated that the asymmetric treatment of porphyrin achieves three goals of creating two secondary coordination sphere(SCS)bulks,maintaining a unique dome deformation,and making atomic out-of-plane deviation.In this way,this metallic complex integrates at least three key features of the pocket structure,the differentiated axial ligations,and the ring distortion,making it an ideal heme analog.
基金financially supported by the National Natural Science Foundation of China(Nos.52203135 and 52273206)Postdoctoral Fellowship Program of CPSF(No.GZC20230372)+4 种基金Huzhou Science and Technology Program Projects(No.2023GZ18)Zhejiang Postdoctoral Research Project(No.ZJ2023133)Science and Technology Cooperation Fund Program of Chengdu-Chinese Academy of ScienceHunan Provincial Natural Science Foundation(No.2021JJ10029)Huxiang High-level Talent Gathering Project(No.2022RC4039)。
文摘Organisms are capable of self-growth through the integration of the nutrients provided by the external environment.This process slows down when they grow.In this study,we mimicked this self-regulated growth via a simple swelling-polymerization strategy in which the stretching polymer chains in the original networks provide entropic elasticity to restrict growth in high growth cycles.Using typical covalently crosslinked polymers,such as acrylamide-based hydrogels and HBA-based elastomers,as examples,we demonstrate that the crosslinked polymers can absorb polymerizable compounds through a swelling-polymerization process to expand their sizes,but the growth extent becomes smaller with increasing growth cycle until reaching a plateau.In addition to their size,these materials become stiffer and exhibit less swelling ability in solvents.Our work not only provides a new growing mode to tune the properties of crosslinked polymers but also discloses the underlying mechanism of crosslinked polymers in multi-cyclic swelling conditions.
基金financial support from NSFC(Nos.21772069 and 21831007)Six Kinds of Talents Project of Jiangsu Province(No.SWYY-025).
文摘A new class of axially chiral aryl-alkene-indole frameworks have been designed,and the first catalytic asymmetric construction of such scaffolds has been established by the strategy of organocatalytic(Z/E)-selective and enantioselective(4+3)cyclization of 3-alkynyl-2-indolylmethanols with 2-naphthols or phenols(all>95:5 E/Z,up to 98% yield,97% ee).This reaction also represents the first catalytic asymmetric construction of axially chiral alkene-heteroaryl scaffolds,which will add a new member to the atropisomeric family.This approach has not only confronted the great challenges in constructing axially chiral alkene-heteroaryl scaffolds but also provided a powerful strategy for the enantioselective construction of axially chiral aryl-alkene-indole frameworks.
基金financial support of the present work by the National Natural Science Foundation of China(Nos.51773056,51603067,21705040)Natural Science Foundationof Hunan Province,China(No.2018JJ3143)+3 种基金China Postdoctoral Science Foundation(Nos.2017M622571,2017M622568 and 2018T110824)Open Project Program of State Key Laboratory of Chemo/Biosensing and Chemometrics(No.2016019)Open Fund of the State Key Laboratory of Luminescent Materials and Devices(South China University of Technology)(No.2019-skllmd-09)Natural Science Foundation of Guangdong Province(No.2017A030313299)。
文摘Direct,in situ selective detection of intracellular formaldehyde(FA)is of great significance for understanding its function in FA-related diseases.Herein,red carbon dots(RCD)are reported as label-free two-photon fluorescent nanoprobes for detecting and imaging of FA.Upon addition of FA,the-NH2 groups of RCD could quickly and specially react with aldehydes to form Schiff base and then the strong fluorescence of RCD with blue-shift emission is recovery due to the destruction of the hydrogen bond interaction between RCD and water.In addition,the nanoprobes exhibit outsta nding photo stability,rapid response(<1 min),high sensitivity(~9.9μmol/L)and excellent selectivity toward FA over other aldehyde group compounds.Notably,owing to the good cell-membrane permeability and biocompatibility,as well as the large two-photon absorption cross-section,the as-prepared RCD can be used as label-free nanoprobes for selectively detecting and imaging FA in living cells and zebrafishes through one-photon and two-photon excitation.Moreover,RCD could stain the tissue of zebrafishes at depths interval of up to 240μm under two-photon excitation.This research implied that RCD are promising tools for directly and in situ imaging FA in vivo,thus providing critical insights into FA-related pathophysiological processes.
基金the National Natural Science Foundation of China (21604021)Hunan Provincial Natural Science Foundation (2018JJ3141)+3 种基金the Innovation Team of Huxiang Highlevel Talent Gathering Engineering (2021RC5028)the National Key Research and Development Program of China (2017YFA0206600)the National Natural Science Foundation of China (51922032 and 21961160720)the open research fund of Songshan Lake Materials Laboratory (2021SLABFK02) for financial support。
文摘Organic solar cells(OSCs)as a promising photovoltaic tech-nology have attracted great attention due to its unique advant-ages,such as solution processing,low cost,lightweight and ex-cellent mechanical flexibility[1−5].Conventional OSCs always employ fullerene derivatives,e.g.
基金This work was supported by the National Natural Science Foundation of China(Grant No.21776067)the Outstanding Youth Foundation of Hunan Province(Grant No.2020JJ2014)+1 种基金the Natural Science Foundation of Hunan Province(Grant Nos.2022JJ30264,2020JJ5159)the Scientific Research Fund of Hunan Provincial Education Department(Grant Nos.20C0803,21B0476).
文摘The industrial application of nano-photocatalysts in wastewater treatment has been severely restricted for a long time due to their difficult separation,poor reusability,and low efficiency.In this work,a facile strategy was proposed to enhance the photocatalytic activity and recovery performance of Ag@AgCl nanocatalysts.Biological veins(Bio-veins)with a unique 3D porous construction were used as carriers for the in-situ growth of Ag@AgCl nanoparticles.Scanning electron microscopy results showed that the Ag@AgCl nanoparticles were uniformly loaded on the surface and interior of the Bio-veins,and the size of the Ag@AgCl nanoparticles immobilized on the Bio-veins(50–300 nm)was significantly smaller than Ag@AgCl obtained by the co-precipitation method(1–3μm).The Bio-veins played a vital role in the photocatalysis reaction system.The degradation efficiency of the Ag@AgCl/Bio-veins(CI4)was up to 3.50 times as high as pure Ag@AgCl.Furthermore,the composites also exhibited excellent recyclability and stability under both visible and solar light.This work provided a suitable strategy for nano-photocatalysts for practical application and may also offer new possibilities for the high-value utilization of biomass materials.
基金This work was supported by the National Natural Science Foundation of China （No. 21575166, and 21372069）, and the Scientific Research Fund of Hunan Provincial Education Department （No. 15K042）.
文摘The reactivity of the metalloporphyrins was closely related to their ligand effect at axial position. The electronic properties of six model Co（II） porphyrins are investigated by spectral and electrochemical methods. Structural parameters of the COOI） complexes are directly obtained from their crystal structures. We demonstrate that the unpaired 3d electron of low-spin Co（II） ions in nonplanar Co（II） porphyrin complexes activated by core contraction of porphyrin macrocycles can be further activated by the axial ligation of imidazole. The activated electron can combine with a n orbital of the porphyrin ring to form a new d-π orbital, which can induce the Q-band of Co（II） porphyrins to visibly split. Addition of imidazole causes the Co（II）/Co（III） and Co（II）/Co（I） reactions to shift to more negative potential. Our results indicate that strong axial ligation and core contraction both play important roles in electron transfer in redox catalysis involving Co（II） complexes.
基金supported by the National Natural Science Foundation of China (21776067)the Outstanding Youth Foundation of Hunan Province (2020JJ2014)+2 种基金Scientific Research Fund of Hunan Provincial Education Department (18C0354 and 20C0803)the National Key Research and Development Program of China (2017YFA0206600)the National Natural Science Foundation of China (51773045, 21772030, 51922032, and 21961160720) for financial support。
文摘Single atom catalysts (SACs), exhibiting outstanding properties for a wide variety of chemical reactions, have become the most active new frontier in heterogeneous catalysis[1]. Benefitting from the uniform coordination environment, every dispersed single atom in SACs can work as active centers to participate in catalytic cycles, presenting the maximum atom utilization efficiency.
基金the National Natural Science Foundation of China (Nos.21802040,21877034)the Natural Science Fund Youth Project of Hunan Province (No.2018JJ3145)+1 种基金the General project of Hunan Education Department(No. 17C0629)the Open Foundation of Key Laboratory of Theoretical Organic Chemistry and Functional Molecule of Ministry of Education,Hunan University of Science and Technology(No. E21843) for financial support
文摘In this review,the recent development about using DESs as green solvents in transition metal catalyzed organic reactions was highlighted.Firstly,the development of DESs was simply introduced.After presenting the advantages of DESs,transition metals catalyzed organic reactions using DESs as green solvents were classified and introduced in detail.Different transition metals such as Au,metal impregnated on magnetite,Pd and Ru catalyzed organic reactions proceeded smoothly in DESs and gave corresponding products in good yields.And in some cases,the catalytic systems could be recycled up to several times without any decrease in activity.
基金the National Natural Science Foundation of China (Nos. 21802040, 21877034)the Natural Science Fund Youth Project of Hunan Province (No. 2018JJ3145)+1 种基金the General project of Hunan Education Department (No. 17C0629)the Open Foundation of Key Laboratory of Theoretical Organic Chemistry and Functional Molecule of Ministry of Education, Hunan University of Science and Technology (No. E21843) for financial support
文摘In this review,the recent development in transition metal catalyzed cross coupling of nitroarenes was highlighted.Firstly,development of transition metal catalyzed cross coupling was simply introduced.After presenting the advantages of nitroarenes,transition metal catalyzed cross coupling using nitroarenes as electrophilic coupling partners was classified and introduced in detail.Based on different chemical bonds such as C–O,C–S,C-C and C–N bonds constructed,different kinds cross coupling of nitroarenes would be highlighted and the plausible reaction mechanism would be presented if available.
基金supported by the Hunan Provincial Natural Science Foundation of China (2019JJ20008)the Construct Program of Applied Characteristic Discipline in Hunan University of Science and Engineering
文摘Quinoxaline-3-carboxylates and analogues are prevalent key structural motifs in bioactive natural products and synthetic drugs.However, the practical protocol for preparation of these motifs from simple raw materials under mild conditions remains rare. In this article, we report a facile protocol for the efficient preparation of various quinoxaline-3-carbonyl compounds(30 examples,63%–92%) through oxidation coupling of quinoxalin-2(1H)-ones with readily available carbazates(or acyl hydrazines) in the presence of K_2S_2O_8 as an oxidant in metal-and base-free conditions. When tert-butyl carbazate was used as the coupling reagent,the decarboxylation product 3-(tert-butyl)-1-methylquinoxalin-2(1H)-one was obtained. The application of this process into a gram-scale synthesis can be easily accomplished. Mechanistic investigations reveal that the functionalization of quinoxalin-2(1H)-ones via a free-radical pathway.
基金supported by the National Natural Science Foundation of China(Nos.22120102002 and 92353301)the Science and Technology Innovation Program of Hunan Province of China(No.2021RC5028).
文摘The clinical approval of platinum-based drugs has prompted the development of novel metallo-complexes during the last several decades,while severe problems,especially for poor water solubility,drug resistance and toxicity in patients,greatly hindered the clinical trials and curative efficacy.To address these issues,the concept of metallo-prodrugs has been proposed for oncology.Some stimuliactivable metallo-prodrugs provide new insights for designing and preparing site-specific prodrugs with maximized therapeutic efficacy and negligible unfavorable by-effects.In this review,recent progress in stimuli-activable metalloprodrugs in the past 20 years has been overviewed,where endogenous and exogenous stimuli have been involved.Typical examples of smart stimuli-activable metallo-prodrugs are discussed regarding to their molecular structure,activation mechanism,and promising biomedical applications.In the end,challenges and future perspectives in metallo-prodrugs have been discussed.
基金supported by the National Natural Science Foundation of China(NSFC,52273206,52173278,and 51833011)Hunan Provincial Natural Science Foundation of China(2021JJ10029,2020JJ3021,and 2021JJ40192)+1 种基金the Open Fund of Hunan Provincial Key Laboratory of Controllable Preparation and Functional Application of Fine Polymers(E22125)the Science and Technology Innovation Program of Hunan Province(2022RC1075 and 2021RC5028)。
基金This work was supported by the National Natural Science Foundation of China(No.21975273)the Scientific Research Starting Foundation of Outstanding Young Scholar of Shandong University,Chinathe Fundamental Research Funds of Shandong University,China.
文摘The interface defects and nickel vacancies of the NiO_(x)lead to interface charge recombination,which limits its application in perovskite solar cells.Here,graphdiyne oxide(GDYO)was added to NiO_(x)as an inorganic hole transporting material.It is found that the average carrier lifetime declined from 29.2 ns to 5.4 ns and the recombination resistance increased significantly after the GDYO adding determined by the time-resolved photoluminescence and electrochemical impedance spectroscopy analysis.We further demonstrated that the GDYO adding to NiO_(x)effectively improved the charge extraction,accelerated the charge transportation and suppressed the charge recombination.Consequently,the optimized NiO_(x)(GDYO)-based cell showed superior performance with a higher fill factor(81.99%)and improved stability with respect to the reference device.This method provides a new method for property regulation of NiO_(x)in inverted planar MAPbI_(3) perovskite solar cells.
