Pitch produced by the lique-faction of coal was divided into two frac-tions:soluble in toluene(TS)and insol-uble in toluene but soluble in pyridine(TI-PS),and their differences in molecu-lar structure and oxidation ac...Pitch produced by the lique-faction of coal was divided into two frac-tions:soluble in toluene(TS)and insol-uble in toluene but soluble in pyridine(TI-PS),and their differences in molecu-lar structure and oxidation activity were studied.Several different carbon materi-als were produced from them by oxida-tion in air(350℃,300 mL/min)fol-lowed by carbonization(1000℃ in Ar),and the effect of the cross-linked structure on their structure and sodium storage properties was investigated.The results showed that the two pitch fractions were obviously different after the air oxidation.The TS fraction with a low degree of condensation and abundant side chains had a stronger oxidation activity and thus introduced more cross-linked oxygen-containing functional groups C(O)―O which prevented carbon layer rearrangement during the carbonization.As a result,a disordered hard carbon with more defects was formed,which improved the electrochemical performance.Therefore,the carbon materials derived from TS(O-TS-1000)had an obvious disordered structure and a larger layer spacing,giving them better sodium storage perform-ance than those derived from the TI-PS fraction(O-TI-PS-1000).The specific capacity of O-TS-1000 was about 250 mAh/g at 20 mA/g,which was 1.67 times higher than that of O-TI-PS-1000(150 mAh/g).展开更多
Two tetrasubstituted carbazole derivatives TBICz and TOXDCz have been designed and synthesized,which possess the twist skeletons and exhibit excellent thermal and morphological stabilities.Utilizing these novel compou...Two tetrasubstituted carbazole derivatives TBICz and TOXDCz have been designed and synthesized,which possess the twist skeletons and exhibit excellent thermal and morphological stabilities.Utilizing these novel compounds as host material,high efficiency solution-processed green phosphorescent organic light-emitting diodes(PhOLEDs)have been achieved.The high triplet energies of TBICz and TOXDCz ensure efficient energy transfer from the host to the phosphor and triplet exciton confinement on the phosphor.Solution-processable green phospho⁃rescent devices employing Ir(ppy)3 as vip and the two tetrasubstituted carbazole derivatives as hosts exhibit high ef⁃ficiencies.The best EL performance is achieved for the TBICz-based device,with a maximum current efficiency of 27.3 cd/A,a maximum power efficiency of 15.9 lm/W,and a maximum external quantum efficiency of 7.8%,which provides more host material options for solution-processed OLEDs.展开更多
We report five coordination polymers(CPs)based on fluorescent ligands[1,6-di(1H-imidazol-1-yl)pyrene(dip),9,10-di(1H-imidazol-1-yl)anthracene(dia)]and anionic ligands[cyclohexane-1,4-dicarboxylic acid(H_(2)cda),campho...We report five coordination polymers(CPs)based on fluorescent ligands[1,6-di(1H-imidazol-1-yl)pyrene(dip),9,10-di(1H-imidazol-1-yl)anthracene(dia)]and anionic ligands[cyclohexane-1,4-dicarboxylic acid(H_(2)cda),camphoric acid(H_(2)cpa)].In[Cd(dip)(cda)]·4H_(2)O}_(n)(1),the Cd^(2+)ions,acting as tetrahedral nodes,are linked by dipand cda^(2-)ligands with four Cd^(2+)ions into five-fold interpenetrating network array of topology of dia.In{[Cd(dip)(cpa)]·4H_(2)O}_(n)(2),the Cd^(2+)ions,acting as a 4-connector,are linked by cpa^(2-)and dip ligands into a 3D framework ofcds topology.In{[Ni(dia)_(2)Cl_(2)]·DMF}_(n)(3),the Ni^(2+)ion is linked by four dia ligands into a layer structure,and 1Dchannels of a cross-section of 1.35 nm×0.96 nm are formed.In{[Cd(dia)_(2)(H_(2)O)_(2)](NO_(3))_(2)·2DMSO}n(4),the dia ligandsconnected Cd^(2+)ions into a 2D layer,and 1D channels are formed between adjacent layers with a cross-section of0.87 nm×0.43 nm.In[Zn(dip)Cl_(2)]_(n)(5),the Zn^(2+)ion is linked by dip ligands into an infinite 1D chain.The infrared,thermal gravimetric,and fluorescent emission data were collected and analyzed for these coordination polymers.CCDC:2356055,1;2440075,2;2356057,3;2356057,4;2356059,5.展开更多
Six coordination polymers based on 9,10-di(pyridine-4-yl)-anthracene(DPA)and 1,6-di(1H-imidazol-1-yl)pyrene(DIP)were obtained by solvothermal reactions.{[Zn(DPA)Cl_(2)]·DMF·2H_(2)O}n(1)and{[Zn_(1.5)(DPA)_(1....Six coordination polymers based on 9,10-di(pyridine-4-yl)-anthracene(DPA)and 1,6-di(1H-imidazol-1-yl)pyrene(DIP)were obtained by solvothermal reactions.{[Zn(DPA)Cl_(2)]·DMF·2H_(2)O}n(1)and{[Zn_(1.5)(DPA)_(1.5)Cl_(3)]·5H_(2)O}n(2)are framework isomers,which both contain zigzag chains formed by DPA,Zn^(2+),and Cl-.The zigzag chains in 1 are further assembled by C—H…Cl interactions into layers,and these layers exhibit two different orientations,displaying a rare 2D to 3D interpenetration mode.The zigzag chains in 2 are parallelly arranged.{[Zn_(3)(DPA)_(3)Br_(6)]·2DMF·_(1.5)H_(2)O}n(3)is isostructural to 2.3 was obtained using ZnBr_(2)instead of ZnCl_(2).[M(DPA)(formate)_(2)(H_(2)O)_(2)]n[M=Co(4),Cu(5)]are isostructural,contain chain structures formed by DPA,Cu^(2+)/Co^(2+),and for-mate ions,which were formed in situ in the solvothermal reaction.{[Zn(DIP)_(2)Cl]ClO_(4)}n(6)contains a layer structure formed by DIP and Zn^(2+).Free DPA and DIP ligands exhibited high fluorescence at room temperature,and coordina-tion polymers 3 and 6 displayed enhanced fluorescent emissions.展开更多
multi-component reaction was reported for the synthesis of 7-ester indoles and bis-indoles under microwave-assisted conditions,enriching and expanding the library of heterocyclic compounds.This reaction started from e...multi-component reaction was reported for the synthesis of 7-ester indoles and bis-indoles under microwave-assisted conditions,enriching and expanding the library of heterocyclic compounds.This reaction started from enamine ketone,aromatic ketone aldehyde hydrate,and carboxylic acid,and selectively synthesized 7-ester indoles and bis-indoles by changing the substituted enamine ketone substrate.This method had the characteristics of high regional selectivity,short reaction time,and green environmental protection.展开更多
An efficient strategy for construction of tricyclic thiazino[3,4-a]isoquinolines has been achieved via 4-dimethylamino-pyridine(DMAP)promoted[5+1]annulation of simple and readily available isoquinoline 1,4-zwitterion ...An efficient strategy for construction of tricyclic thiazino[3,4-a]isoquinolines has been achieved via 4-dimethylamino-pyridine(DMAP)promoted[5+1]annulation of simple and readily available isoquinoline 1,4-zwitterion withα-bromoketone.This protocol showed good substrate compatibility as an array of structurally and electronically diverse thiazino[3,4-a]isoquinolines prepared efficiently in moderate to good yields.It is particularly emphasized that although this reaction exhibits moderate stereoselectivity,the two diastereomers can be separated by column chromatography,providing an important molecular diversity foundation for the screening and structural optimization of subsequent drug lead compounds,as well as a simple and efficient method for constructing complex nitrogen-containing and sulfur-containing heterocyclic compounds.It has potential application value in the fields of medicinal chemistry and organic synthesis.展开更多
Introduction The generation of biological wastes such as cow dung and aloe vera waste(AVW)causes a serious ecological pollution.The microbial electrolytic cell coupled with anaerobic digestion(MEC-AD)system can make a...Introduction The generation of biological wastes such as cow dung and aloe vera waste(AVW)causes a serious ecological pollution.The microbial electrolytic cell coupled with anaerobic digestion(MEC-AD)system can make a rational utilization of these biodegradable organic wastes,which is of vital importance for alleviating environmental deterioration and reducing resource waste.Electrode materials and accelerants are the two major factors that affect methane production in the MEC-AD system.They affect microbial attachment and electron transfer in the MEC-AD system.Bio-based carbon materials are carbon materials prepared from biomass as raw materials.They have characteristics such as a rich pore structure,good chemical stability,biocompatibility,and controllable surface properties,which can be used as accelerants and electrodes in the MEC-AD system to optimize its performance.This study was to investigate the influence of biomass-derived carbon as an electrode and accelerant on the performance of the MEC-AD system,and the mechanism for increasing the production of biogas and methane was also analyzed,thus providing a basis for the multifunctional application of biomass-derived carbon in the MEC-AD system.Methods A series of experimental methods were adopted to study the MEC-AD system.Two types of bio-based carbon,i.e.,aloe vera waste derived spherical carbon(AVW-SC)and porous carbon(AVW-PC),were synthesized via hydrothermal carbonization.The raw AVW material was washed with water,dried,ground,and subjected to hydrothermal treatment to obtain AVW-SC.After activating AVW-SC with KOH,it was carbonized in a tube furnace to obtain AVW-PC.In the preparation of the electrodes,bio-based carbon(AVW-SC and AVW-PC)was mixed with 5%polytetrafluoroethylene powder in ethanol and deionized water,and then ground in a ball mill for 4 h to form a slurry.The slurry was evenly sprayed on the Ti mesh,dried and sintered in N2 atmosphere at 360℃to obtain Ti-SC and Ti-PC electrodes.Four groups of experiments were conducted to determine the optimal voltage,compare different carbon electrodes,and explore the optimal coating amount.The MEC-AD reactor adopted 500 mL wide-mouthed glass bottles with a working volume of 400 mL.Each MEC-AD system received a co-substrate mixture of cattle dung and aloe vera waste and inoculum of sewage sludge in a mass ratio of 3:7.Afterward,they were placed at(36±1)℃for 35 d.The biogas was collected by a water displacement method.The materials were analyzed by characterization techniques such as X-ray diffraction(XRD)and scanning electron microscopy(SEM),and electrochemical tests were conducted on different electrodes.The composition,pH,TS,VS,TCOD and nutrient content of biogas were analyzed by standard chemical methods.Microbial community analysis was conducted using high-throughput sequencing technology.The modified Gompertz model was adopted to predict the kinetic parameters,and the coulombic efficiency and methane recovery rate were calculated according to a specific formula.Results and discussion The result shows that AVW-SC is spherical and closely aggregated,while AVW-PC has a three-dimensional network structure,with average pore diameter of 9.77 nm.The electron exchange capacity(EEC)of AVW-PC(i.e.,0.75μmol·e-/g)is higher than that of AVW-SC(i.e.,0.15μmol·e-/g),indicating a better electron exchange capacity.These results indicate that AVW-PC provides more substrate and bacteria accumulation sites,and has better electron-donating and electron-accepting ability,thus improving the digestion efficiency.In the MEC-AD system,using Ti mesh as an electrode,the effect of different voltages(i.e.,0,0.4,0.6,0.8 V and 1.2 V)on the system performance is investigated,obtaining the optimum biogas production and organic matter degradation rate at 0.8 V.AVW-SC and AVW-PC are respectively coated on Ti mesh as electrodes.The results show that the MEC-AD system with AVW-PC coated Ti mesh as the electrode has a better performance.The electrochemical analysis shows that the electrode coated with AVW-PC has a larger specific capacitance and a smaller charge transfer resistance,indicating that AVW-PC can improve the electrochemical properties and electron transfer ability of MEC-AD system.The influence of coating amount(i.e.,0.025,0.05,0.10,0.15,and 0.20 g)of AVW-PC on the MEC-AD system is investigated.At a coating amount of AVW-PC of 0.1 g,the cumulative biogas production and methane content of the Ti_(0.8)-PC_90.1) group both reach the maximum values.Different doses of AVW-PC(i.e.,0.10%,0.15%,0.20%,and 0.25%)are added as accelerants in Ti_(0.8)-PC_90.1).At the addition amount of AVW-PC of 0.20%,the Ti_(0.8)-PC_90.1)/PC0.2 group performs the optimum biogas production(i.e.,633.63 mL/g VS),methane content(i.e.,65.85%),and total nutrient content of biogas residue(i.e.,42.30 g/kg).In Ti_(0.8)-PC_90.1)/PC0.2,Bacteroidales,Pseudomonadales,Oscillospirales,Methanobacteraceae,Methanospirillaceae,Methanosarcinacea and Methanosaetaceae significantly increase.The increase in microbial diversity promotes interspecific hydrogen transfer(IHT),interspecific acetic transfer(IAT),and direct interspecific electron transfer(DIET),thereby enhancing methanogenic efficiency.Conclusions AVW-SC and AVW-PC were utilized as electrodes and accelerants to enhance methane yield in MEC-AD system.The Ti mesh electrode coated with different concentrations of AVW-PC achieved the optimal biogas production at 0.8 V.Specifically,the Ti_(0.8)-PC_90.1) combination could generate the maximum total amount of biogas and methane proportion.The Ti_(0.8)-PC_90.1)/PC0.2 combination exhibited the optimum performance(i.e.,biogas yield of 633.63 mL/g VS,methane content of 65.85%and total nutritional content of 42.30 g/kg).High abundances of Bacteroidales,Pseudomonadales,Oscillospirales,Methanobacteraceae,Methanospirillaceae,Methanosarcinaceae,and Methanosaetaceae appeared in the Ti_(0.8)-PC_90.1)/PC0.2 group,compared to other groups.In addition,an increased microbial diversity led to an enhanced methane production through processes like DIET.This research could highlight the potential significance of AVW-PC as both electrode and accelerator for increasing methane production and provide a perspective for improving MEC-AD performance through multiple applications of biomass-derived carbon.展开更多
Changes to the microstructure of a hard carbon(HC)and its solid electrolyte interface(SEI)can be effective in improving the electrode kinetics.However,achieving fast charging using a simple and inexpensive strategy wi...Changes to the microstructure of a hard carbon(HC)and its solid electrolyte interface(SEI)can be effective in improving the electrode kinetics.However,achieving fast charging using a simple and inexpensive strategy without sacrificing its initial Coulombic efficiency remains a challenge in sodium ion batteries.A simple liquid-phase coating approach has been used to generate a pitch-derived soft carbon layer on the HC surface,and its effect on the porosity of HC and SEI chemistry has been studied.A variety of structural characterizations show a soft carbon coating can increase the defect and ultra-micropore contents.The increase in ultra-micropore comes from both the soft carbon coatings and the larger pores within the HC that are partially filled by pitch,which provides more Na+storage sites.In-situ FTIR/EIS and ex-situ XPS showed that the soft carbon coating induced the formation of thinner SEI that is richer in NaF from the electrolyte,which stabilized the interface and promoted the charge transfer process.As a result,the anode produced fastcharging(329.8 mAh g^(−1)at 30 mA g^(−1)and 198.6 mAh g^(−1)at 300 mA g^(−1))and had a better cycling performance(a high capacity retention of 81.4%after 100 cycles at 150 mA g^(−1)).This work reveals the critical role of coating layer in changing the pore structure,SEI chemistry and diffusion kinetics of hard carbon,which enables rational design of sodium-ion battery anode with enhanced fast charging capability.展开更多
Chronic obstructive pulmonary disease(COPD)has garnered increased attention as a result of its persistent symptoms,which undermine patientsʼquality of life.Fudosteine has substantial advantages in the treatment of COP...Chronic obstructive pulmonary disease(COPD)has garnered increased attention as a result of its persistent symptoms,which undermine patientsʼquality of life.Fudosteine has substantial advantages in the treatment of COPD due to its high efficacy and low adverse effects.In this study,Fudosteine sulfonamide derivatives Series I and amine derivatives Series II were designed and synthesized,and their biological activities were evaluated.The results showed that compound 6f had outstanding anti-inflammatory action with an IC_(50) of 1.08 mmol/L,and a higher antioxidant capacity than the lead molecule.At the same time,molecular docking investigations have revealed that compound 6f establishes hydrogen bonds and hydrophobic contacts with the MUC5AC protein.Furthermore,derivative 1f inhibited PDE4A1 enzyme activity five times more than Fudosteine.2,2-Diphenyl-1-picrylhydrazyl(DPPH)free radical scavenging tests demonstrated that all examined substances had higher antioxidant activity than Fudosteine.This study established a solid foundation for further research into COPD drug therapy.展开更多
Tin phosphide(Sn_(x)P_(y))is an anode for sodium-ion batteries resulting from its exceptionally high theoretical capacity in future.Nevertheless,its application will be hindered by significant volume expansion during ...Tin phosphide(Sn_(x)P_(y))is an anode for sodium-ion batteries resulting from its exceptionally high theoretical capacity in future.Nevertheless,its application will be hindered by significant volume expansion during charge discharge cycles and poor electrical conductivity.This study employs a Sn-based metal-organic framework(Sn-MOF)as a precursor for synthesizing tin phosphide nanoparticles.Then Solidago Canadensis L.,commonly known as Canadian Goldenrod,is utilized as a biomass carbon carrier to form a composite with tin phosphide nanoparticles.The biomass derived porous carbon provides additional sodium ion storage sites and serves as a structural scaffold that constrains the volumetric expansion of tin phosphide,thereby enhancing the material’s stability.The fabricated composite exhibits superior electrode electrochemical performance for sodium-ion batteries.It retains a high capacity(489.5 mA·h/g)after 100 cycles at 0.2 A/g.Even after 500 cycles at a high current density of 2 A/g,it still maintains a stable reversible capacity.This study offers a comprehensive exploration of innovative design strategies essential for the development of novel anode materials,paving the way for more sustainable and efficient sodium-ion-based energy storage systems.展开更多
Graphene and its derivatives are two-dimensional nanomaterials with exceptional physical and chemical properties.Research has shown that their addition can counter the inherent deficiencies of cementbased composites,i...Graphene and its derivatives are two-dimensional nanomaterials with exceptional physical and chemical properties.Research has shown that their addition can counter the inherent deficiencies of cementbased composites,including low tensile strength,poor toughness,and high susceptibility to cracking.However,because of its high specific surface area and the van der Waals force between layers,graphene is prone to agglomerate in the cement matrix which can make the properties worse.Hence,improving the graphene dispersion is essential.The surface structure and properties of graphene and its derivatives are first introduced,and the different methods for their dispersion in cement-based materials are reviewed.Their effects on the mechanical properties and durability of cement-based materials are then summarized.Based on these results,the microscopic and nanoscopic mechanisms of the way graphene and its derivatives affect cement-based materials are elaborated.Current problems and future trends in this research area are then considered.展开更多
A transition-metal-free strategy for the synthesis of carboline derivatives via sequential dual C—N bond formation in a one-pot reaction is reported.Using 2,2'-dihalogenated pyridyl biaryls and primary amines as ...A transition-metal-free strategy for the synthesis of carboline derivatives via sequential dual C—N bond formation in a one-pot reaction is reported.Using 2,2'-dihalogenated pyridyl biaryls and primary amines as starting materials,this method efficiently constructs a series ofα-,β-,γ-andδ-carbolines under alkaline conditions.The reaction proceeds smoothly in the presence of lithium tert-butoxide(t-BuOLi)or cesium carbonate(Cs_(2)CO_(3))without requiring transition metal catalysts,demonstrating good functional group tolerance.This approach enables gram-scale synthesis and has been successfully applied to the preparation of the organic material 2,6-CbPy,achieving high conversion efficiency.展开更多
The ability to replicate the microenvironment of the human body through the fabrication of scaffolds is a significant achievement in the biomedical field.However,the search for the ideal scaffold is still in its infan...The ability to replicate the microenvironment of the human body through the fabrication of scaffolds is a significant achievement in the biomedical field.However,the search for the ideal scaffold is still in its infancy and there are significant challenges to overcome.In the modern era,the scientific community is increasingly turned to natural substances due to their superior biological ability,lower cost,biodegradability,and lower toxicity than synthetic lab-made products.Chitosan is a well-known polysaccharide that has recently garnered a high amount of attention for its biological activities,especially in 3D bone tissue engineering.Chitosan closely matches the native tissues and thus stands out as a popular candidate for bioprinting.This review focuses on the potential of chitosan-based scaffolds for advancements and the drawbacks in bone treatment.Chitosan-based nanocomposites have exhibited strong mechanical strength,water-trapping ability,cellular interaction,and biodegradability.Chitosan derivatives have also encouraged and provided different routes for treatment and enhanced biological activities.3D tailored bioprinting has opened new doors for designing and manufacturing scaffolds with biological,mechanical,and topographical properties.展开更多
The selective hydrogenation ofα,β-unsaturated aldehydes/ketones enables precise control over product structures and properties by regulating hydrogen transport pathways and bond cleavage sequences to selectively red...The selective hydrogenation ofα,β-unsaturated aldehydes/ketones enables precise control over product structures and properties by regulating hydrogen transport pathways and bond cleavage sequences to selectively reduce C=C or C=O bonds while preserving other functional groups within the molecule.This approach serves as a critical strategy for the directional synthesis of high-value molecules.However,achieving such selectivity remains challenging due to the thermodynamic equilibrium and kinetic competition between C=O and C=C bonds inα,β-unsaturated systems.Consequently,constructing precisely targeted catalytic systems is essential to overcome these limitations,offering both fundamental scientific significance and industrial application potential.Metal-organic frameworks(MOFs)and their derivatives have emerged as innovative platforms for designing such systems,owing to their programmable topology,tunable pore microenvironments,spatially controllable active sites,and modifiable electronic structures.This review systematically summarizes the research progress of MOF-based catalysts for selec-tive hydrogenation ofα,β-unsaturated aldehydes/ketones in the last decade,with emphasis on the design strategy,conformational relationship,and catalytic mechanism,aiming to provide new ideas for the design of targeted catalyt-ic systems for the selective hydrogenation ofα,β-unsaturated aldehydes/ketones.展开更多
A new photocatalytic annulative acylative difunctionalization of 1,6-enynes is reported,enabling stereoselective access to acylated 1-indanones with cyclic quaternary centers in moderate to good yields.This photocatal...A new photocatalytic annulative acylative difunctionalization of 1,6-enynes is reported,enabling stereoselective access to acylated 1-indanones with cyclic quaternary centers in moderate to good yields.This photocatalysis enables two types of acylation of unsaturated hydrocarbons by adjusting the categories of acyl radical precursors.Aroyl chlorides as bifunctional reagents react with 1,6-enynes to realize annulative chloroacylation,while acyl oxime esters are used as acyl radical precursors,which undergo a three-component annulative alkoxyacylation by treatment with 1,6-enynes and alcohols.The current method demonstrates good functional group compatibility,a broad substrate scope and mild reaction conditions.展开更多
文摘Pitch produced by the lique-faction of coal was divided into two frac-tions:soluble in toluene(TS)and insol-uble in toluene but soluble in pyridine(TI-PS),and their differences in molecu-lar structure and oxidation activity were studied.Several different carbon materi-als were produced from them by oxida-tion in air(350℃,300 mL/min)fol-lowed by carbonization(1000℃ in Ar),and the effect of the cross-linked structure on their structure and sodium storage properties was investigated.The results showed that the two pitch fractions were obviously different after the air oxidation.The TS fraction with a low degree of condensation and abundant side chains had a stronger oxidation activity and thus introduced more cross-linked oxygen-containing functional groups C(O)―O which prevented carbon layer rearrangement during the carbonization.As a result,a disordered hard carbon with more defects was formed,which improved the electrochemical performance.Therefore,the carbon materials derived from TS(O-TS-1000)had an obvious disordered structure and a larger layer spacing,giving them better sodium storage perform-ance than those derived from the TI-PS fraction(O-TI-PS-1000).The specific capacity of O-TS-1000 was about 250 mAh/g at 20 mA/g,which was 1.67 times higher than that of O-TI-PS-1000(150 mAh/g).
文摘Two tetrasubstituted carbazole derivatives TBICz and TOXDCz have been designed and synthesized,which possess the twist skeletons and exhibit excellent thermal and morphological stabilities.Utilizing these novel compounds as host material,high efficiency solution-processed green phosphorescent organic light-emitting diodes(PhOLEDs)have been achieved.The high triplet energies of TBICz and TOXDCz ensure efficient energy transfer from the host to the phosphor and triplet exciton confinement on the phosphor.Solution-processable green phospho⁃rescent devices employing Ir(ppy)3 as vip and the two tetrasubstituted carbazole derivatives as hosts exhibit high ef⁃ficiencies.The best EL performance is achieved for the TBICz-based device,with a maximum current efficiency of 27.3 cd/A,a maximum power efficiency of 15.9 lm/W,and a maximum external quantum efficiency of 7.8%,which provides more host material options for solution-processed OLEDs.
文摘We report five coordination polymers(CPs)based on fluorescent ligands[1,6-di(1H-imidazol-1-yl)pyrene(dip),9,10-di(1H-imidazol-1-yl)anthracene(dia)]and anionic ligands[cyclohexane-1,4-dicarboxylic acid(H_(2)cda),camphoric acid(H_(2)cpa)].In[Cd(dip)(cda)]·4H_(2)O}_(n)(1),the Cd^(2+)ions,acting as tetrahedral nodes,are linked by dipand cda^(2-)ligands with four Cd^(2+)ions into five-fold interpenetrating network array of topology of dia.In{[Cd(dip)(cpa)]·4H_(2)O}_(n)(2),the Cd^(2+)ions,acting as a 4-connector,are linked by cpa^(2-)and dip ligands into a 3D framework ofcds topology.In{[Ni(dia)_(2)Cl_(2)]·DMF}_(n)(3),the Ni^(2+)ion is linked by four dia ligands into a layer structure,and 1Dchannels of a cross-section of 1.35 nm×0.96 nm are formed.In{[Cd(dia)_(2)(H_(2)O)_(2)](NO_(3))_(2)·2DMSO}n(4),the dia ligandsconnected Cd^(2+)ions into a 2D layer,and 1D channels are formed between adjacent layers with a cross-section of0.87 nm×0.43 nm.In[Zn(dip)Cl_(2)]_(n)(5),the Zn^(2+)ion is linked by dip ligands into an infinite 1D chain.The infrared,thermal gravimetric,and fluorescent emission data were collected and analyzed for these coordination polymers.CCDC:2356055,1;2440075,2;2356057,3;2356057,4;2356059,5.
文摘Six coordination polymers based on 9,10-di(pyridine-4-yl)-anthracene(DPA)and 1,6-di(1H-imidazol-1-yl)pyrene(DIP)were obtained by solvothermal reactions.{[Zn(DPA)Cl_(2)]·DMF·2H_(2)O}n(1)and{[Zn_(1.5)(DPA)_(1.5)Cl_(3)]·5H_(2)O}n(2)are framework isomers,which both contain zigzag chains formed by DPA,Zn^(2+),and Cl-.The zigzag chains in 1 are further assembled by C—H…Cl interactions into layers,and these layers exhibit two different orientations,displaying a rare 2D to 3D interpenetration mode.The zigzag chains in 2 are parallelly arranged.{[Zn_(3)(DPA)_(3)Br_(6)]·2DMF·_(1.5)H_(2)O}n(3)is isostructural to 2.3 was obtained using ZnBr_(2)instead of ZnCl_(2).[M(DPA)(formate)_(2)(H_(2)O)_(2)]n[M=Co(4),Cu(5)]are isostructural,contain chain structures formed by DPA,Cu^(2+)/Co^(2+),and for-mate ions,which were formed in situ in the solvothermal reaction.{[Zn(DIP)_(2)Cl]ClO_(4)}n(6)contains a layer structure formed by DIP and Zn^(2+).Free DPA and DIP ligands exhibited high fluorescence at room temperature,and coordina-tion polymers 3 and 6 displayed enhanced fluorescent emissions.
文摘multi-component reaction was reported for the synthesis of 7-ester indoles and bis-indoles under microwave-assisted conditions,enriching and expanding the library of heterocyclic compounds.This reaction started from enamine ketone,aromatic ketone aldehyde hydrate,and carboxylic acid,and selectively synthesized 7-ester indoles and bis-indoles by changing the substituted enamine ketone substrate.This method had the characteristics of high regional selectivity,short reaction time,and green environmental protection.
文摘An efficient strategy for construction of tricyclic thiazino[3,4-a]isoquinolines has been achieved via 4-dimethylamino-pyridine(DMAP)promoted[5+1]annulation of simple and readily available isoquinoline 1,4-zwitterion withα-bromoketone.This protocol showed good substrate compatibility as an array of structurally and electronically diverse thiazino[3,4-a]isoquinolines prepared efficiently in moderate to good yields.It is particularly emphasized that although this reaction exhibits moderate stereoselectivity,the two diastereomers can be separated by column chromatography,providing an important molecular diversity foundation for the screening and structural optimization of subsequent drug lead compounds,as well as a simple and efficient method for constructing complex nitrogen-containing and sulfur-containing heterocyclic compounds.It has potential application value in the fields of medicinal chemistry and organic synthesis.
文摘Introduction The generation of biological wastes such as cow dung and aloe vera waste(AVW)causes a serious ecological pollution.The microbial electrolytic cell coupled with anaerobic digestion(MEC-AD)system can make a rational utilization of these biodegradable organic wastes,which is of vital importance for alleviating environmental deterioration and reducing resource waste.Electrode materials and accelerants are the two major factors that affect methane production in the MEC-AD system.They affect microbial attachment and electron transfer in the MEC-AD system.Bio-based carbon materials are carbon materials prepared from biomass as raw materials.They have characteristics such as a rich pore structure,good chemical stability,biocompatibility,and controllable surface properties,which can be used as accelerants and electrodes in the MEC-AD system to optimize its performance.This study was to investigate the influence of biomass-derived carbon as an electrode and accelerant on the performance of the MEC-AD system,and the mechanism for increasing the production of biogas and methane was also analyzed,thus providing a basis for the multifunctional application of biomass-derived carbon in the MEC-AD system.Methods A series of experimental methods were adopted to study the MEC-AD system.Two types of bio-based carbon,i.e.,aloe vera waste derived spherical carbon(AVW-SC)and porous carbon(AVW-PC),were synthesized via hydrothermal carbonization.The raw AVW material was washed with water,dried,ground,and subjected to hydrothermal treatment to obtain AVW-SC.After activating AVW-SC with KOH,it was carbonized in a tube furnace to obtain AVW-PC.In the preparation of the electrodes,bio-based carbon(AVW-SC and AVW-PC)was mixed with 5%polytetrafluoroethylene powder in ethanol and deionized water,and then ground in a ball mill for 4 h to form a slurry.The slurry was evenly sprayed on the Ti mesh,dried and sintered in N2 atmosphere at 360℃to obtain Ti-SC and Ti-PC electrodes.Four groups of experiments were conducted to determine the optimal voltage,compare different carbon electrodes,and explore the optimal coating amount.The MEC-AD reactor adopted 500 mL wide-mouthed glass bottles with a working volume of 400 mL.Each MEC-AD system received a co-substrate mixture of cattle dung and aloe vera waste and inoculum of sewage sludge in a mass ratio of 3:7.Afterward,they were placed at(36±1)℃for 35 d.The biogas was collected by a water displacement method.The materials were analyzed by characterization techniques such as X-ray diffraction(XRD)and scanning electron microscopy(SEM),and electrochemical tests were conducted on different electrodes.The composition,pH,TS,VS,TCOD and nutrient content of biogas were analyzed by standard chemical methods.Microbial community analysis was conducted using high-throughput sequencing technology.The modified Gompertz model was adopted to predict the kinetic parameters,and the coulombic efficiency and methane recovery rate were calculated according to a specific formula.Results and discussion The result shows that AVW-SC is spherical and closely aggregated,while AVW-PC has a three-dimensional network structure,with average pore diameter of 9.77 nm.The electron exchange capacity(EEC)of AVW-PC(i.e.,0.75μmol·e-/g)is higher than that of AVW-SC(i.e.,0.15μmol·e-/g),indicating a better electron exchange capacity.These results indicate that AVW-PC provides more substrate and bacteria accumulation sites,and has better electron-donating and electron-accepting ability,thus improving the digestion efficiency.In the MEC-AD system,using Ti mesh as an electrode,the effect of different voltages(i.e.,0,0.4,0.6,0.8 V and 1.2 V)on the system performance is investigated,obtaining the optimum biogas production and organic matter degradation rate at 0.8 V.AVW-SC and AVW-PC are respectively coated on Ti mesh as electrodes.The results show that the MEC-AD system with AVW-PC coated Ti mesh as the electrode has a better performance.The electrochemical analysis shows that the electrode coated with AVW-PC has a larger specific capacitance and a smaller charge transfer resistance,indicating that AVW-PC can improve the electrochemical properties and electron transfer ability of MEC-AD system.The influence of coating amount(i.e.,0.025,0.05,0.10,0.15,and 0.20 g)of AVW-PC on the MEC-AD system is investigated.At a coating amount of AVW-PC of 0.1 g,the cumulative biogas production and methane content of the Ti_(0.8)-PC_90.1) group both reach the maximum values.Different doses of AVW-PC(i.e.,0.10%,0.15%,0.20%,and 0.25%)are added as accelerants in Ti_(0.8)-PC_90.1).At the addition amount of AVW-PC of 0.20%,the Ti_(0.8)-PC_90.1)/PC0.2 group performs the optimum biogas production(i.e.,633.63 mL/g VS),methane content(i.e.,65.85%),and total nutrient content of biogas residue(i.e.,42.30 g/kg).In Ti_(0.8)-PC_90.1)/PC0.2,Bacteroidales,Pseudomonadales,Oscillospirales,Methanobacteraceae,Methanospirillaceae,Methanosarcinacea and Methanosaetaceae significantly increase.The increase in microbial diversity promotes interspecific hydrogen transfer(IHT),interspecific acetic transfer(IAT),and direct interspecific electron transfer(DIET),thereby enhancing methanogenic efficiency.Conclusions AVW-SC and AVW-PC were utilized as electrodes and accelerants to enhance methane yield in MEC-AD system.The Ti mesh electrode coated with different concentrations of AVW-PC achieved the optimal biogas production at 0.8 V.Specifically,the Ti_(0.8)-PC_90.1) combination could generate the maximum total amount of biogas and methane proportion.The Ti_(0.8)-PC_90.1)/PC0.2 combination exhibited the optimum performance(i.e.,biogas yield of 633.63 mL/g VS,methane content of 65.85%and total nutritional content of 42.30 g/kg).High abundances of Bacteroidales,Pseudomonadales,Oscillospirales,Methanobacteraceae,Methanospirillaceae,Methanosarcinaceae,and Methanosaetaceae appeared in the Ti_(0.8)-PC_90.1)/PC0.2 group,compared to other groups.In addition,an increased microbial diversity led to an enhanced methane production through processes like DIET.This research could highlight the potential significance of AVW-PC as both electrode and accelerator for increasing methane production and provide a perspective for improving MEC-AD performance through multiple applications of biomass-derived carbon.
基金National Key Research and Development Program of China(2022YFE0206300)National Natural Science Foundation of China(U21A2081,22075074,22209047)+2 种基金Guangdong Basic and Applied Basic Research Foundation(2024A1515011620)Hunan Provincial Natural Science Foundation of China(2024JJ5068)Foundation of Yuelushan Center for Industrial Innovation(2023YCII0119)。
文摘Changes to the microstructure of a hard carbon(HC)and its solid electrolyte interface(SEI)can be effective in improving the electrode kinetics.However,achieving fast charging using a simple and inexpensive strategy without sacrificing its initial Coulombic efficiency remains a challenge in sodium ion batteries.A simple liquid-phase coating approach has been used to generate a pitch-derived soft carbon layer on the HC surface,and its effect on the porosity of HC and SEI chemistry has been studied.A variety of structural characterizations show a soft carbon coating can increase the defect and ultra-micropore contents.The increase in ultra-micropore comes from both the soft carbon coatings and the larger pores within the HC that are partially filled by pitch,which provides more Na+storage sites.In-situ FTIR/EIS and ex-situ XPS showed that the soft carbon coating induced the formation of thinner SEI that is richer in NaF from the electrolyte,which stabilized the interface and promoted the charge transfer process.As a result,the anode produced fastcharging(329.8 mAh g^(−1)at 30 mA g^(−1)and 198.6 mAh g^(−1)at 300 mA g^(−1))and had a better cycling performance(a high capacity retention of 81.4%after 100 cycles at 150 mA g^(−1)).This work reveals the critical role of coating layer in changing the pore structure,SEI chemistry and diffusion kinetics of hard carbon,which enables rational design of sodium-ion battery anode with enhanced fast charging capability.
文摘Chronic obstructive pulmonary disease(COPD)has garnered increased attention as a result of its persistent symptoms,which undermine patientsʼquality of life.Fudosteine has substantial advantages in the treatment of COPD due to its high efficacy and low adverse effects.In this study,Fudosteine sulfonamide derivatives Series I and amine derivatives Series II were designed and synthesized,and their biological activities were evaluated.The results showed that compound 6f had outstanding anti-inflammatory action with an IC_(50) of 1.08 mmol/L,and a higher antioxidant capacity than the lead molecule.At the same time,molecular docking investigations have revealed that compound 6f establishes hydrogen bonds and hydrophobic contacts with the MUC5AC protein.Furthermore,derivative 1f inhibited PDE4A1 enzyme activity five times more than Fudosteine.2,2-Diphenyl-1-picrylhydrazyl(DPPH)free radical scavenging tests demonstrated that all examined substances had higher antioxidant activity than Fudosteine.This study established a solid foundation for further research into COPD drug therapy.
文摘Tin phosphide(Sn_(x)P_(y))is an anode for sodium-ion batteries resulting from its exceptionally high theoretical capacity in future.Nevertheless,its application will be hindered by significant volume expansion during charge discharge cycles and poor electrical conductivity.This study employs a Sn-based metal-organic framework(Sn-MOF)as a precursor for synthesizing tin phosphide nanoparticles.Then Solidago Canadensis L.,commonly known as Canadian Goldenrod,is utilized as a biomass carbon carrier to form a composite with tin phosphide nanoparticles.The biomass derived porous carbon provides additional sodium ion storage sites and serves as a structural scaffold that constrains the volumetric expansion of tin phosphide,thereby enhancing the material’s stability.The fabricated composite exhibits superior electrode electrochemical performance for sodium-ion batteries.It retains a high capacity(489.5 mA·h/g)after 100 cycles at 0.2 A/g.Even after 500 cycles at a high current density of 2 A/g,it still maintains a stable reversible capacity.This study offers a comprehensive exploration of innovative design strategies essential for the development of novel anode materials,paving the way for more sustainable and efficient sodium-ion-based energy storage systems.
文摘Graphene and its derivatives are two-dimensional nanomaterials with exceptional physical and chemical properties.Research has shown that their addition can counter the inherent deficiencies of cementbased composites,including low tensile strength,poor toughness,and high susceptibility to cracking.However,because of its high specific surface area and the van der Waals force between layers,graphene is prone to agglomerate in the cement matrix which can make the properties worse.Hence,improving the graphene dispersion is essential.The surface structure and properties of graphene and its derivatives are first introduced,and the different methods for their dispersion in cement-based materials are reviewed.Their effects on the mechanical properties and durability of cement-based materials are then summarized.Based on these results,the microscopic and nanoscopic mechanisms of the way graphene and its derivatives affect cement-based materials are elaborated.Current problems and future trends in this research area are then considered.
基金Project supported by the National Natural Science Foundation of China(No.22371303)the Zhongshan Municipal Bureau of Science and Technology(Nos.2021B2014,CXTD2022013)the Shanghai Rising-Star Program(21QA1411000)。
文摘A transition-metal-free strategy for the synthesis of carboline derivatives via sequential dual C—N bond formation in a one-pot reaction is reported.Using 2,2'-dihalogenated pyridyl biaryls and primary amines as starting materials,this method efficiently constructs a series ofα-,β-,γ-andδ-carbolines under alkaline conditions.The reaction proceeds smoothly in the presence of lithium tert-butoxide(t-BuOLi)or cesium carbonate(Cs_(2)CO_(3))without requiring transition metal catalysts,demonstrating good functional group tolerance.This approach enables gram-scale synthesis and has been successfully applied to the preparation of the organic material 2,6-CbPy,achieving high conversion efficiency.
文摘The ability to replicate the microenvironment of the human body through the fabrication of scaffolds is a significant achievement in the biomedical field.However,the search for the ideal scaffold is still in its infancy and there are significant challenges to overcome.In the modern era,the scientific community is increasingly turned to natural substances due to their superior biological ability,lower cost,biodegradability,and lower toxicity than synthetic lab-made products.Chitosan is a well-known polysaccharide that has recently garnered a high amount of attention for its biological activities,especially in 3D bone tissue engineering.Chitosan closely matches the native tissues and thus stands out as a popular candidate for bioprinting.This review focuses on the potential of chitosan-based scaffolds for advancements and the drawbacks in bone treatment.Chitosan-based nanocomposites have exhibited strong mechanical strength,water-trapping ability,cellular interaction,and biodegradability.Chitosan derivatives have also encouraged and provided different routes for treatment and enhanced biological activities.3D tailored bioprinting has opened new doors for designing and manufacturing scaffolds with biological,mechanical,and topographical properties.
文摘The selective hydrogenation ofα,β-unsaturated aldehydes/ketones enables precise control over product structures and properties by regulating hydrogen transport pathways and bond cleavage sequences to selectively reduce C=C or C=O bonds while preserving other functional groups within the molecule.This approach serves as a critical strategy for the directional synthesis of high-value molecules.However,achieving such selectivity remains challenging due to the thermodynamic equilibrium and kinetic competition between C=O and C=C bonds inα,β-unsaturated systems.Consequently,constructing precisely targeted catalytic systems is essential to overcome these limitations,offering both fundamental scientific significance and industrial application potential.Metal-organic frameworks(MOFs)and their derivatives have emerged as innovative platforms for designing such systems,owing to their programmable topology,tunable pore microenvironments,spatially controllable active sites,and modifiable electronic structures.This review systematically summarizes the research progress of MOF-based catalysts for selec-tive hydrogenation ofα,β-unsaturated aldehydes/ketones in the last decade,with emphasis on the design strategy,conformational relationship,and catalytic mechanism,aiming to provide new ideas for the design of targeted catalyt-ic systems for the selective hydrogenation ofα,β-unsaturated aldehydes/ketones.
文摘A new photocatalytic annulative acylative difunctionalization of 1,6-enynes is reported,enabling stereoselective access to acylated 1-indanones with cyclic quaternary centers in moderate to good yields.This photocatalysis enables two types of acylation of unsaturated hydrocarbons by adjusting the categories of acyl radical precursors.Aroyl chlorides as bifunctional reagents react with 1,6-enynes to realize annulative chloroacylation,while acyl oxime esters are used as acyl radical precursors,which undergo a three-component annulative alkoxyacylation by treatment with 1,6-enynes and alcohols.The current method demonstrates good functional group compatibility,a broad substrate scope and mild reaction conditions.
