A visible-light induced cascade sulfonation/cyclization reaction of 3-allyl-2-arylquinazolinones employing water as an environmentally friendly solvent was revealed.This transition metal-free protocol,using 9-mesityl-...A visible-light induced cascade sulfonation/cyclization reaction of 3-allyl-2-arylquinazolinones employing water as an environmentally friendly solvent was revealed.This transition metal-free protocol,using 9-mesityl-10-methylacridinium perchlorate as the photocatalyst,represents a masterly tactic for the synthesis of sulfonated dihydroisoquinolino[1,2-b]quinazolinones featuring mild conditions,facile operation,and broad substrate scope.展开更多
A novel polyetheretherketone (PEK-C) prepared from phenolphthalein has been synthesized. In order to improve some of its properties for application in high performance membrane, the PEK-C has been sulfonated with conc...A novel polyetheretherketone (PEK-C) prepared from phenolphthalein has been synthesized. In order to improve some of its properties for application in high performance membrane, the PEK-C has been sulfonated with concentrated sulfuric acid. Degree of sulfonation can be regulated by controlling the temmperature and time of sulfonation. The characterization of the sulfonated PEK-C in sodium salt form has been made by IR, ~1H NMR and ^(13)C NMR etc. It is shown that the sulfonation appears to take place exclusively in the ortho position to phenolic ether of phenolphthalein unit. The result is in agreement with theoretical deduction. Some properties of the sulfonated PEK-C, such as solubility, transition temperature, thermal degradation and hydrophilicity have also been discussed.展开更多
Proton exchange membrane(PEM)is an integral component in fuel cells which enables proton transport for efficient energy conversion.Sulfonated Polyether Ether Ketone(SPEEK)has emerged as a cost-effective option with no...Proton exchange membrane(PEM)is an integral component in fuel cells which enables proton transport for efficient energy conversion.Sulfonated Polyether Ether Ketone(SPEEK)has emerged as a cost-effective option with non-fluorinated aromatic backbones for Proton Exchange Membrane Fuel Cell(PEMFC)applications,even though it exhibits lower proton conductivity compared to Nafion.This work aims to study the influence of Sulfonated Chitosan(SCS)concentrations on proton conductivity of SPEEK-based PEM at room temperature.SPEEK was synthesized using a sulfonation process with concentrated sulfuric acid at room temperature.SCS was synthesized via reflux of CS and 1.2 M H2SO4 with a ratio of 1:35(w/v)at 90℃ for 30 min.The composite membranes of SPEEK-SCS were formed with four different SCS concentrations,using the solution castingmethod,andDimethyl Sulfoxide(DMSO)was used as a solvent.The composite membranes synthesized include pure SPEEK(S0),SPEEK with 1%SCS(S1),SPEEK with 2%SCS(S2),and SPEEK with 3%SCS(S3).Fourier transform infrared spectroscopy(FTIR),X-ray diffraction(XRD),water uptake,degree of swelling,Ionic exchange capacity(IEC)with Electrochemical impedance spectroscopy(EIS)were used to characterize the composite membranes in terms of composition,crystallinity,water absorption,dimensional changes,number of exchangeable ions in membranes,and proton conductivity,respectively.Notably,S3 had the highest water uptake and the lowest degree of swelling.S2 had the highest proton conductivity among the SPEEK-SCS composite membranes at room temperature with 3.44×10^(−2) Scm^(-1).展开更多
Biopolymeric nanocomposites have attracted considerable attention because of their biocompatibility,biodegradability,and unique physicochemical properties.It is essential to manufacture three-dimensional(3D)biocompati...Biopolymeric nanocomposites have attracted considerable attention because of their biocompatibility,biodegradability,and unique physicochemical properties.It is essential to manufacture three-dimensional(3D)biocompatible micro/nanostructures using biopolymeric nanocomposites.Herein,we demonstrate the high-fidelity fabrication of biocompatible 3D features with sub-50 nm resolution using femtosecond laser direct writing(FsLDW)of a biopolymeric nanocomposite composed of egg white and sulfonated graphene(S-graphene).The biopolymer nanocomposite acts as a negative photoresist suitable for water-based lithography.The introduction of S-graphene not only dramatically lowered the laser power threshold but also significantly modulated the morphology of the 3D features constructed by FsLDW.Microstructures with porous,rough,or smooth morphologies were obtained by optimizing the S-graphene concentration and laser scanning speed.The fabricated egg-white/S-graphene microstructures exhibited biocompatibility and environmental degradability.Egg white/S-graphene was also employed to fabricate diffractive gratings with superior optical quality.This study provides a promising method to manufacture biocompatible 3D features with controllable morphology,which has potential applications in biological and photonic fields.展开更多
Poly(aryl ether sulfone)with fatty-acid side chains that crosslink with epoxy resin improves the interfacial compatibility between poly(aryl ether sulfone)and epoxy resin.Hydroxyl-terminated phenolphthalein-based poly...Poly(aryl ether sulfone)with fatty-acid side chains that crosslink with epoxy resin improves the interfacial compatibility between poly(aryl ether sulfone)and epoxy resin.Hydroxyl-terminated phenolphthalein-based poly(aryl ether sulfone)(PPES-OH)was blended with fatty-acid side-chain-modified phenolphthalein-based poly(aryl ether sulfone)(PPES-TA),with the goal of further enhancing the toughening effect on epoxy resin.In this study,PPES-OH,PPES-TA,and a composite poly(aryl ether sulfone)(PESP-TA)were synthesized.Their molecular structures and thermal properties were characterized using proton nuclear magnetic resonance spectroscopy(1H-NMR spectroscopy),thermogravimetric analysis(TGA),and differential scanning calorimetry(DSC).Subsequently,PPES-OH,PPES-TA,and PESP-TA were introduced into the anhydride-cured epoxy system to evaluate their toughening effects on epoxy resin.The curing behavior of the epoxy resin blends was investigated using DSC,which also enabled the exploration of the corresponding curing mechanisms.The thermal and mechanical properties of the toughened systems were characterized.Scanning electron microscopy(SEM)was used to observe the impact fracture surfaces of the resin,which revealed‘fish-scale’structures and shear bands in the resin system after curing.These findings demonstrate that similar thermoplastic chains become entangled with one another,forming additional physical cross-links.This enhanced the interfacial compatibility between the thermoplastic and thermoset resins,which,in turn,significantly improved the impact toughness and elongation at break of the system.In summary,PESP-TA has emerged as a reactive thermoplastic toughening agent that is feasible for preparation and has significant practical application potential.展开更多
To precisely control intrachain π-electron delocalization and interchain interaction simultaneously is the prerequisite to obtain stable and efficient deep-blue light-emitting p-n polymer semiconductors for the polym...To precisely control intrachain π-electron delocalization and interchain interaction simultaneously is the prerequisite to obtain stable and efficient deep-blue light-emitting p-n polymer semiconductors for the polymer light-emitting diodes(PLEDs).Herein,we introduced the steric carbazole-fluorene nanogrid into light-emitting diphenyl sulfone-based p-n polymer semiconductors(PG and PDG) via metal-free C-N coupling polymerization for the fabrication of deep-blue PLEDs.The steric,rigid and twisted configuration between nanogrid and diphenyl sulfone in PG and PDG present the unique characteristic of large steric hindrance interaction to suppress interchain aggregation in solid state.Due to the different length of electron-deficient diphenyl sulfone monomers,PG showed a deep-blue emission with a maximum peak at 428 nm but red-shifted to 480 nm for the PDG films.Interestingly,similar deep-blue emission behavior of PG in diluted non-polar solution and films suggested the extremely weak interchain aggregation.Finally,PLEDs based on PG are fabricated with a stable deep-blue emission of CIE(0.15,0.10),and corresponding EL spectral profile is also completely identical to PL ones of diluted solution,revealed the intrachain emission without obvious interchain excited state,confirmed effectiveness of the steric hindrance functionalization of nanogrid in p-n polymer semiconductor for deep-blue light-emitting organic optoelectronics.展开更多
基金funds from Natural Science Foundation of Guangxi Province(Nos.2023GXNSFBA026304,2023GXNSFDA026063)the Guangxi Science and Technology Base and Special Talents(No.Guike AD20159047).
文摘A visible-light induced cascade sulfonation/cyclization reaction of 3-allyl-2-arylquinazolinones employing water as an environmentally friendly solvent was revealed.This transition metal-free protocol,using 9-mesityl-10-methylacridinium perchlorate as the photocatalyst,represents a masterly tactic for the synthesis of sulfonated dihydroisoquinolino[1,2-b]quinazolinones featuring mild conditions,facile operation,and broad substrate scope.
文摘A novel polyetheretherketone (PEK-C) prepared from phenolphthalein has been synthesized. In order to improve some of its properties for application in high performance membrane, the PEK-C has been sulfonated with concentrated sulfuric acid. Degree of sulfonation can be regulated by controlling the temmperature and time of sulfonation. The characterization of the sulfonated PEK-C in sodium salt form has been made by IR, ~1H NMR and ^(13)C NMR etc. It is shown that the sulfonation appears to take place exclusively in the ortho position to phenolic ether of phenolphthalein unit. The result is in agreement with theoretical deduction. Some properties of the sulfonated PEK-C, such as solubility, transition temperature, thermal degradation and hydrophilicity have also been discussed.
文摘Proton exchange membrane(PEM)is an integral component in fuel cells which enables proton transport for efficient energy conversion.Sulfonated Polyether Ether Ketone(SPEEK)has emerged as a cost-effective option with non-fluorinated aromatic backbones for Proton Exchange Membrane Fuel Cell(PEMFC)applications,even though it exhibits lower proton conductivity compared to Nafion.This work aims to study the influence of Sulfonated Chitosan(SCS)concentrations on proton conductivity of SPEEK-based PEM at room temperature.SPEEK was synthesized using a sulfonation process with concentrated sulfuric acid at room temperature.SCS was synthesized via reflux of CS and 1.2 M H2SO4 with a ratio of 1:35(w/v)at 90℃ for 30 min.The composite membranes of SPEEK-SCS were formed with four different SCS concentrations,using the solution castingmethod,andDimethyl Sulfoxide(DMSO)was used as a solvent.The composite membranes synthesized include pure SPEEK(S0),SPEEK with 1%SCS(S1),SPEEK with 2%SCS(S2),and SPEEK with 3%SCS(S3).Fourier transform infrared spectroscopy(FTIR),X-ray diffraction(XRD),water uptake,degree of swelling,Ionic exchange capacity(IEC)with Electrochemical impedance spectroscopy(EIS)were used to characterize the composite membranes in terms of composition,crystallinity,water absorption,dimensional changes,number of exchangeable ions in membranes,and proton conductivity,respectively.Notably,S3 had the highest water uptake and the lowest degree of swelling.S2 had the highest proton conductivity among the SPEEK-SCS composite membranes at room temperature with 3.44×10^(−2) Scm^(-1).
基金financially supported by the National Key Research and Development Program of China(Nos.2024YFB4607402 and 2016YFC1100502)the National Natural Science Foundation of China(Nos.51673208 and 61975213)。
文摘Biopolymeric nanocomposites have attracted considerable attention because of their biocompatibility,biodegradability,and unique physicochemical properties.It is essential to manufacture three-dimensional(3D)biocompatible micro/nanostructures using biopolymeric nanocomposites.Herein,we demonstrate the high-fidelity fabrication of biocompatible 3D features with sub-50 nm resolution using femtosecond laser direct writing(FsLDW)of a biopolymeric nanocomposite composed of egg white and sulfonated graphene(S-graphene).The biopolymer nanocomposite acts as a negative photoresist suitable for water-based lithography.The introduction of S-graphene not only dramatically lowered the laser power threshold but also significantly modulated the morphology of the 3D features constructed by FsLDW.Microstructures with porous,rough,or smooth morphologies were obtained by optimizing the S-graphene concentration and laser scanning speed.The fabricated egg-white/S-graphene microstructures exhibited biocompatibility and environmental degradability.Egg white/S-graphene was also employed to fabricate diffractive gratings with superior optical quality.This study provides a promising method to manufacture biocompatible 3D features with controllable morphology,which has potential applications in biological and photonic fields.
基金financially supported by the Science and Technology Innovation Development Program of Jilin City(Nos.20240103013 and 20240103012)the Jilin Province Key Breakthrough Special Project(No.2025JLGJ0015GX)the Open Project of the State Key Laboratory of Inorganic Synthesis and Preparative Chemistry(No.202527)at Jilin University.The authors acknowledge the assistance of the Jilin Institute of Chemical Technology Center of Characterization and Analysis.We also thank Pro.Jie Chen with the help of SEM characterization.
文摘Poly(aryl ether sulfone)with fatty-acid side chains that crosslink with epoxy resin improves the interfacial compatibility between poly(aryl ether sulfone)and epoxy resin.Hydroxyl-terminated phenolphthalein-based poly(aryl ether sulfone)(PPES-OH)was blended with fatty-acid side-chain-modified phenolphthalein-based poly(aryl ether sulfone)(PPES-TA),with the goal of further enhancing the toughening effect on epoxy resin.In this study,PPES-OH,PPES-TA,and a composite poly(aryl ether sulfone)(PESP-TA)were synthesized.Their molecular structures and thermal properties were characterized using proton nuclear magnetic resonance spectroscopy(1H-NMR spectroscopy),thermogravimetric analysis(TGA),and differential scanning calorimetry(DSC).Subsequently,PPES-OH,PPES-TA,and PESP-TA were introduced into the anhydride-cured epoxy system to evaluate their toughening effects on epoxy resin.The curing behavior of the epoxy resin blends was investigated using DSC,which also enabled the exploration of the corresponding curing mechanisms.The thermal and mechanical properties of the toughened systems were characterized.Scanning electron microscopy(SEM)was used to observe the impact fracture surfaces of the resin,which revealed‘fish-scale’structures and shear bands in the resin system after curing.These findings demonstrate that similar thermoplastic chains become entangled with one another,forming additional physical cross-links.This enhanced the interfacial compatibility between the thermoplastic and thermoset resins,which,in turn,significantly improved the impact toughness and elongation at break of the system.In summary,PESP-TA has emerged as a reactive thermoplastic toughening agent that is feasible for preparation and has significant practical application potential.
基金the support from the Jiangsu Provincial Senior Talent Program (Dengfeng,Jiangsu University)the support from the National Key R&D Program of China (No.2024YFB3612600)+3 种基金the National Natural Science Foundation of China (Nos.22275098,62288102)Basic Research Program of Jiangsu (No.BK20243057)the Natural Science Research Start-up Foundation of Recruiting Talents of Nanjing University of Posts and Telecommunications (No.NY222097)the National Natural Science Foundation of China (No.62205035)。
文摘To precisely control intrachain π-electron delocalization and interchain interaction simultaneously is the prerequisite to obtain stable and efficient deep-blue light-emitting p-n polymer semiconductors for the polymer light-emitting diodes(PLEDs).Herein,we introduced the steric carbazole-fluorene nanogrid into light-emitting diphenyl sulfone-based p-n polymer semiconductors(PG and PDG) via metal-free C-N coupling polymerization for the fabrication of deep-blue PLEDs.The steric,rigid and twisted configuration between nanogrid and diphenyl sulfone in PG and PDG present the unique characteristic of large steric hindrance interaction to suppress interchain aggregation in solid state.Due to the different length of electron-deficient diphenyl sulfone monomers,PG showed a deep-blue emission with a maximum peak at 428 nm but red-shifted to 480 nm for the PDG films.Interestingly,similar deep-blue emission behavior of PG in diluted non-polar solution and films suggested the extremely weak interchain aggregation.Finally,PLEDs based on PG are fabricated with a stable deep-blue emission of CIE(0.15,0.10),and corresponding EL spectral profile is also completely identical to PL ones of diluted solution,revealed the intrachain emission without obvious interchain excited state,confirmed effectiveness of the steric hindrance functionalization of nanogrid in p-n polymer semiconductor for deep-blue light-emitting organic optoelectronics.