In this study, Fe-doped TiO2/SiO2 （Fe@TS） nanofibrous membranes with molecular imprinted modification, were fabricated by a combination of sol-gel process, electrospinning, calcination and liquid phase deposition te...In this study, Fe-doped TiO2/SiO2 （Fe@TS） nanofibrous membranes with molecular imprinted modification, were fabricated by a combination of sol-gel process, electrospinning, calcination and liquid phase deposition techniques, The precursor sol was prepared from one-pot condensation of poly （vinylpyrrolidone）, ferric chloride hexahydrate, tetraethyl orthosilicate and titanium n-butoxide in the mixture solvents of N,N-dimethylformamide and ethyl alcohol. Fibrous membrane wasthen fabricated by electrospinning, followed by calcination to form the Fe@TS composite. The physicochemical properties of Fe@TS were characterized. Thereafter, 4-nitrophenol （4NP） was used as the template to deposit onto nanofibrous Fe@TS membranes, with a thin layer of molecular imprinted polymer in liquid phase. The photodegradation capabilities of 4NP and methyl orange wereexamined in both single and binary systems. The results demonstrated that molecular imprinted Fe@TS membranes exhibited excellent selectivity for photodegradation of 4NP.展开更多
In this study, nanofibrous polypyrrole-coated TiO2/SiO2 （PPy@TS） membranes were fabricated by a combination of sol-gel process, electrospinning, calcination, and in situ polymerization. Samples from the electrospinn...In this study, nanofibrous polypyrrole-coated TiO2/SiO2 （PPy@TS） membranes were fabricated by a combination of sol-gel process, electrospinning, calcination, and in situ polymerization. Samples from the electrospinning, calcination, and in situ polymerization steps were characterized by scanning electron microscopy, transmission electron microscopy, X-ray diffraction, Fourier transform infrared spectrosco- py, and thermogravimetry. The in situ polymerization of PPy is aimed to enhance the overall photocatalytic capability of TiO2 in the TiO2/SiO2 composite fibers. Results of the photocatalytic degradation tests demonstrated that the PPy@TS composites possess enhanced photocatalytic activity for the degradation of methyl orange.展开更多
Simple and efficient stereo-selective synthesis of exo-5-norbornene-2-carboxylic acid (NBCA) is reported. Preliminary studies on base promoted isomerization of methyl 5-norbornene-2-carboxylate (MNBC) revealed that ra...Simple and efficient stereo-selective synthesis of exo-5-norbornene-2-carboxylic acid (NBCA) is reported. Preliminary studies on base promoted isomerization of methyl 5-norbornene-2-carboxylate (MNBC) revealed that rapid isomerization was accomplished with sodium tert-butoxide (tBuONa), and the exo-content at the equilibrium was ca. 60%. The hydrolyses of endo-rich MNBC (endo/exo = 80/20) under various conditions were carried out. The exo selectivity for resulting NBCA was improved when the hydrolysis was conducted with equimolar water at room temperature in the presence of the stronger base (tBuONa) (endo/exo: 18/82). Whereas the use of excess amount of water led to rapid and non-selective hydrolysis affording high endo content of the product. The plausible reaction mechanism involving rapid equilibrium of thermodynamic isomerization and kinetically preferred hydrolysis of exo ester is proposed.展开更多
Hybrids consisting of a microporous film and polymeric microspheres were fabricated via a simple method without a special apparatus. Highly ordered microporous polymer films with honeycomb structure were fabricated by...Hybrids consisting of a microporous film and polymeric microspheres were fabricated via a simple method without a special apparatus. Highly ordered microporous polymer films with honeycomb structure were fabricated by a dissipative process utilizing amphiphilic poly(acrylic acid)- block-polystyrene, which was synthesized by atom transfer radical polymerization followed by an acid-catalyzed ester cleavage reaction. In order to embed the microsphere efficiently, the dried microporous films should be soaked in methanol to alter the surface functionality and to improve the wettability of the film surface. The introduction of amino functionality to polystyrene microspheres by seeded polymerization of N,N-dimethylaminoethyl methacrylate drastically improved the embedding efficiency. The effect of open pore size was also investigated.展开更多
Micron-sized polymer particles from single poly(4-butyltriphenylamine) (PBTPA) homopolymer, binary polymer blend [PBTPA/poly(methyl methacrylate) (PMMA)], and ternary polymer blend (PBTPA/PBTPA-b-PMMA/PMMA) via a solv...Micron-sized polymer particles from single poly(4-butyltriphenylamine) (PBTPA) homopolymer, binary polymer blend [PBTPA/poly(methyl methacrylate) (PMMA)], and ternary polymer blend (PBTPA/PBTPA-b-PMMA/PMMA) via a solvent evaporation method, and the surface morphologies and inside structure of resulting particles were investigated. Spherical homopolymer particles with smooth surface were resulted from PBTPA with low molecular weight. In the case of binary blends (PBTPA/PMMA = 1/1), Janus (low molecular weight) and dumbbell (high molecular weight) type morphologies were observed. The particles based on ternary blends containing PBTPA-b-PMMA showed core-shell type morphologies (PMMA;core, PBTPA;shell). Degree of engulfment of PMMArich domain increased with the content of the block copolymer. The decrease of domain size was not observed although the block copolymer had a suitable structure as a compatibilizer for the blend. It was also found that the initial concentration of polymer solution had an effect on the final morphology.展开更多
Poly(4-butyltriarylamine)s with t-butyldimethylsilyl terminal protecting group (PBTPA-TBS) with various molecular weights were prepared by C-N coupling polymerization. The resulting precursors were postfunctionalized ...Poly(4-butyltriarylamine)s with t-butyldimethylsilyl terminal protecting group (PBTPA-TBS) with various molecular weights were prepared by C-N coupling polymerization. The resulting precursors were postfunctionalized and subse- quently used as macroinitiators for atom transfer radial polymerization (ATRP) of n-butyl acrylate (n-BA) and ethyl acrylate (EA). Both the polymerization processes were controlled and the polymers were characterized by 1H NMR, gel permeation chromatography (GPC) and thermal properties, which confirmed the successful synthesis of all the poly-mers. The microphase separated behaviors of the poly (4-butyltriarylamine)-block-poly (butyl acrylate) (PBTPA-b-PBA) were examined by AFM in the film showing phase separation structures for all the polymers. The photorefractive property of the composite based on PBTPA-b-PBA block copolymer was evaluated by two-beam coupling experiment. A relative high gain coefficient of 42.7 cm?1 was obtained at the electric field of 31 V/?m.展开更多
Electroluminescent characteristics were investigated for the blue emitting devices fabricated with the blend systems consisting of hole transporting polytriarylamine (PTAA), electron transporting polyfluorene (PF), an...Electroluminescent characteristics were investigated for the blue emitting devices fabricated with the blend systems consisting of hole transporting polytriarylamine (PTAA), electron transporting polyfluorene (PF), and a block copolymer with both segments (PF-b-PTAA) as an active layer in order to elucidate the relationship between the chemical nature and morphology of the active layer, and EL performance. The addition of PF-b-PTAA to PF homopolymer afforded the hole injecting and/or electron blocking ability to increase the efficiency. The addition to PF/PTAA blend keeping the chemical composition constant also improved the performance by controlling the morphology and/or the domain size in phase-separated films.展开更多
Microspheres based on binary polymer blend consisting of polystyrene (PSt), poly (methyl methacrylate) (PMMA), block copolymer comprising PSt and PMMA subunits, and ternary polymer blend consisting of PSt, PMMA, and b...Microspheres based on binary polymer blend consisting of polystyrene (PSt), poly (methyl methacrylate) (PMMA), block copolymer comprising PSt and PMMA subunits, and ternary polymer blend consisting of PSt, PMMA, and block copolymer were fabricated by a solvent evaporation method, in which a polymer solution in dichloromethane was dispersed in water phase with the aid of a homogenizer to obtain an O/W emulsion followed by solvent evaporation with agitation to solidify the polymer. In the case of ternary blend, the effect of block copolymer content on the morphology of resulting spheres was investigated. Ternary blends afforded the bi-compartmental morphologies, the intermediate morphology between Janus and core-shell, which was confirmed by TEM observation. Seed polymerization of St or MMA was also carried out utilizing the resulting microspheres as seed particles in order to control the shape, and the surface morphology of particles. The particles with snowman-like morphology were obtained by seed polymerization of St using PSt/PMMA binary blend microspheres as seed particles. Surface roughness was controlled by the polymerization of MMA in the block copolymer seed, and that of St in the ternary blend seed.展开更多
In order to mimic hierarchical nanostructures in nature,particles of polymer blends consisting of poly(4-butyltriphenylamine)(PBTPA),poly(methyl methacrylate)(PMMA)and PBTPA-block-PMMA were fabricated by a solvent eva...In order to mimic hierarchical nanostructures in nature,particles of polymer blends consisting of poly(4-butyltriphenylamine)(PBTPA),poly(methyl methacrylate)(PMMA)and PBTPA-block-PMMA were fabricated by a solvent evaporation method.Effects of the molecular weight and the chemical composition of PBTPA-b-PMMA,molecular weights of homopolymers,and the composition of the blend on the morphology were investigated.The polymer blend particle consisting of PBTPA and PMMA homopolymers exhibited thermodynamically favored core-shell structure,in which more hydrophilic PMMA-shell surrounded PBTPA-core.The addition of 10 wt%of PBTPA-b-PMMA caused the morphological transition from core-shell toJanus or inversed core-shell,in which PBTPA-shell surrounded PMMA-core,depending on the molecular weight of PBTPA segment in PBTPA-b-PMMA.When the molecular weight of PMMA segment was higher than that of PMMA homopolymer,watermelon-like particles in which small PBTPA domain less than 80 nm dispersed in the PMMA domain surrounded by PBTPA shell were observed.As the ratio of PBTPA-b-PMMA increased,the interface of the macrophase separation became obscure.At 50 wt%of the PBTPA-b-PMMA,only microphase separation was observed.The measurement of interfacial tension by pendant drop method demonstrated that PBTPA-b-PMMA lower the interfacial tension between PBTPA and the aqueous phase to the value similar to that of PMMA with the aqueous phase.展开更多
Current attempts in vaccine delivery systems concentrate on replicating the natural dissemination of live pathogens,but neglect that pathogens evolve to evade the immune system rather than to provoke it.In the case of...Current attempts in vaccine delivery systems concentrate on replicating the natural dissemination of live pathogens,but neglect that pathogens evolve to evade the immune system rather than to provoke it.In the case of enveloped RNA viruses,it is the natural dissemination of nucleocapsid protein(NP,core antigen)and surface antigen that delays NP exposure to immune surveillance.Here,we report a multi-layered aluminum hydroxide-stabilized emulsion(MASE)to dictate the delivery sequence of the antigens.In this manner,the receptor-binding domain(RBD,surface antigen)of the spike protein was trapped inside the nanocavity,while NP was absorbed on the outside of the droplets,enabling the burst release of NP before RBD.Compared with the natural packaging strategy,the inside-out strategy induced potent type I interferon-mediated innate immune responses and triggered an immune-potentiated environment in advance,which subsequently boosted CD40+DC activations and the engagement of the lymph nodes.In both H1N1 influenza and SARS-CoV-2 vaccines,rMASE significantly increased antigen-specific antibody secretion,memory T cell engagement,and Th1-biased immune response,which diminished viral loads after lethal challenge.By simply reversing the delivery sequence of the surface antigen and core antigen,the inside-out strategy may offer major implications for enhanced vaccinations against the enveloped RNA virus.展开更多
基金supported by the National Natural Science Foundation of China(No. 51503083)China Postdoctoral Science Foundation(No. 2017M611696)+1 种基金the Fundamental Research Funds for the Central Universities(No. JUSRP51723B)the National High-tech R&D Program of China(No.2016YFB0302901)
文摘In this study, Fe-doped TiO2/SiO2 （Fe@TS） nanofibrous membranes with molecular imprinted modification, were fabricated by a combination of sol-gel process, electrospinning, calcination and liquid phase deposition techniques, The precursor sol was prepared from one-pot condensation of poly （vinylpyrrolidone）, ferric chloride hexahydrate, tetraethyl orthosilicate and titanium n-butoxide in the mixture solvents of N,N-dimethylformamide and ethyl alcohol. Fibrous membrane wasthen fabricated by electrospinning, followed by calcination to form the Fe@TS composite. The physicochemical properties of Fe@TS were characterized. Thereafter, 4-nitrophenol （4NP） was used as the template to deposit onto nanofibrous Fe@TS membranes, with a thin layer of molecular imprinted polymer in liquid phase. The photodegradation capabilities of 4NP and methyl orange wereexamined in both single and binary systems. The results demonstrated that molecular imprinted Fe@TS membranes exhibited excellent selectivity for photodegradation of 4NP.
基金supported by National Natural Science Foundation of China(No.51503083)the Fundamental Research Funds for the Central Universities(No. JUSRP51723B)the National Hightech R&D Program of China (No. 2016YFB0302901)
文摘In this study, nanofibrous polypyrrole-coated TiO2/SiO2 （PPy@TS） membranes were fabricated by a combination of sol-gel process, electrospinning, calcination, and in situ polymerization. Samples from the electrospinning, calcination, and in situ polymerization steps were characterized by scanning electron microscopy, transmission electron microscopy, X-ray diffraction, Fourier transform infrared spectrosco- py, and thermogravimetry. The in situ polymerization of PPy is aimed to enhance the overall photocatalytic capability of TiO2 in the TiO2/SiO2 composite fibers. Results of the photocatalytic degradation tests demonstrated that the PPy@TS composites possess enhanced photocatalytic activity for the degradation of methyl orange.
文摘Simple and efficient stereo-selective synthesis of exo-5-norbornene-2-carboxylic acid (NBCA) is reported. Preliminary studies on base promoted isomerization of methyl 5-norbornene-2-carboxylate (MNBC) revealed that rapid isomerization was accomplished with sodium tert-butoxide (tBuONa), and the exo-content at the equilibrium was ca. 60%. The hydrolyses of endo-rich MNBC (endo/exo = 80/20) under various conditions were carried out. The exo selectivity for resulting NBCA was improved when the hydrolysis was conducted with equimolar water at room temperature in the presence of the stronger base (tBuONa) (endo/exo: 18/82). Whereas the use of excess amount of water led to rapid and non-selective hydrolysis affording high endo content of the product. The plausible reaction mechanism involving rapid equilibrium of thermodynamic isomerization and kinetically preferred hydrolysis of exo ester is proposed.
文摘Hybrids consisting of a microporous film and polymeric microspheres were fabricated via a simple method without a special apparatus. Highly ordered microporous polymer films with honeycomb structure were fabricated by a dissipative process utilizing amphiphilic poly(acrylic acid)- block-polystyrene, which was synthesized by atom transfer radical polymerization followed by an acid-catalyzed ester cleavage reaction. In order to embed the microsphere efficiently, the dried microporous films should be soaked in methanol to alter the surface functionality and to improve the wettability of the film surface. The introduction of amino functionality to polystyrene microspheres by seeded polymerization of N,N-dimethylaminoethyl methacrylate drastically improved the embedding efficiency. The effect of open pore size was also investigated.
文摘Micron-sized polymer particles from single poly(4-butyltriphenylamine) (PBTPA) homopolymer, binary polymer blend [PBTPA/poly(methyl methacrylate) (PMMA)], and ternary polymer blend (PBTPA/PBTPA-b-PMMA/PMMA) via a solvent evaporation method, and the surface morphologies and inside structure of resulting particles were investigated. Spherical homopolymer particles with smooth surface were resulted from PBTPA with low molecular weight. In the case of binary blends (PBTPA/PMMA = 1/1), Janus (low molecular weight) and dumbbell (high molecular weight) type morphologies were observed. The particles based on ternary blends containing PBTPA-b-PMMA showed core-shell type morphologies (PMMA;core, PBTPA;shell). Degree of engulfment of PMMArich domain increased with the content of the block copolymer. The decrease of domain size was not observed although the block copolymer had a suitable structure as a compatibilizer for the blend. It was also found that the initial concentration of polymer solution had an effect on the final morphology.
文摘Poly(4-butyltriarylamine)s with t-butyldimethylsilyl terminal protecting group (PBTPA-TBS) with various molecular weights were prepared by C-N coupling polymerization. The resulting precursors were postfunctionalized and subse- quently used as macroinitiators for atom transfer radial polymerization (ATRP) of n-butyl acrylate (n-BA) and ethyl acrylate (EA). Both the polymerization processes were controlled and the polymers were characterized by 1H NMR, gel permeation chromatography (GPC) and thermal properties, which confirmed the successful synthesis of all the poly-mers. The microphase separated behaviors of the poly (4-butyltriarylamine)-block-poly (butyl acrylate) (PBTPA-b-PBA) were examined by AFM in the film showing phase separation structures for all the polymers. The photorefractive property of the composite based on PBTPA-b-PBA block copolymer was evaluated by two-beam coupling experiment. A relative high gain coefficient of 42.7 cm?1 was obtained at the electric field of 31 V/?m.
文摘Electroluminescent characteristics were investigated for the blue emitting devices fabricated with the blend systems consisting of hole transporting polytriarylamine (PTAA), electron transporting polyfluorene (PF), and a block copolymer with both segments (PF-b-PTAA) as an active layer in order to elucidate the relationship between the chemical nature and morphology of the active layer, and EL performance. The addition of PF-b-PTAA to PF homopolymer afforded the hole injecting and/or electron blocking ability to increase the efficiency. The addition to PF/PTAA blend keeping the chemical composition constant also improved the performance by controlling the morphology and/or the domain size in phase-separated films.
文摘Microspheres based on binary polymer blend consisting of polystyrene (PSt), poly (methyl methacrylate) (PMMA), block copolymer comprising PSt and PMMA subunits, and ternary polymer blend consisting of PSt, PMMA, and block copolymer were fabricated by a solvent evaporation method, in which a polymer solution in dichloromethane was dispersed in water phase with the aid of a homogenizer to obtain an O/W emulsion followed by solvent evaporation with agitation to solidify the polymer. In the case of ternary blend, the effect of block copolymer content on the morphology of resulting spheres was investigated. Ternary blends afforded the bi-compartmental morphologies, the intermediate morphology between Janus and core-shell, which was confirmed by TEM observation. Seed polymerization of St or MMA was also carried out utilizing the resulting microspheres as seed particles in order to control the shape, and the surface morphology of particles. The particles with snowman-like morphology were obtained by seed polymerization of St using PSt/PMMA binary blend microspheres as seed particles. Surface roughness was controlled by the polymerization of MMA in the block copolymer seed, and that of St in the ternary blend seed.
基金supported by Institute of Global Innovation Research in Tokyo University of Agriculture and Technology(TUAT).
文摘In order to mimic hierarchical nanostructures in nature,particles of polymer blends consisting of poly(4-butyltriphenylamine)(PBTPA),poly(methyl methacrylate)(PMMA)and PBTPA-block-PMMA were fabricated by a solvent evaporation method.Effects of the molecular weight and the chemical composition of PBTPA-b-PMMA,molecular weights of homopolymers,and the composition of the blend on the morphology were investigated.The polymer blend particle consisting of PBTPA and PMMA homopolymers exhibited thermodynamically favored core-shell structure,in which more hydrophilic PMMA-shell surrounded PBTPA-core.The addition of 10 wt%of PBTPA-b-PMMA caused the morphological transition from core-shell toJanus or inversed core-shell,in which PBTPA-shell surrounded PMMA-core,depending on the molecular weight of PBTPA segment in PBTPA-b-PMMA.When the molecular weight of PMMA segment was higher than that of PMMA homopolymer,watermelon-like particles in which small PBTPA domain less than 80 nm dispersed in the PMMA domain surrounded by PBTPA shell were observed.As the ratio of PBTPA-b-PMMA increased,the interface of the macrophase separation became obscure.At 50 wt%of the PBTPA-b-PMMA,only microphase separation was observed.The measurement of interfacial tension by pendant drop method demonstrated that PBTPA-b-PMMA lower the interfacial tension between PBTPA and the aqueous phase to the value similar to that of PMMA with the aqueous phase.
基金supported by the National Key Research and Development Program of China(2021YFE020527,2021YFC2302605,2021YFC2300142),"From 0 to 1"Original Innovation Project of Basic Frontier Scientific Research Program of Chinese Academy of Sciences(ZDBS-LY-SLH040)Bejing Nova Program(Z201100006820139)the Foundation for Innovative Research Groups of the National Natural Science Foundation of China(Grant No.21821005)+4 种基金CAS Project for Young Scientists in Basic Research(YSBR-010)the Pilot Project of Chinese Academy of Sciences(Grant No.XDB29040303)The National Natural Science Fund for Outstanding Young Scholar(T2222022)National Natural Science Foundation of China(Grant No.32030062),Youth Innovation Promotion Association of the Chinese Academy of Sciences(NO.2020000053)the foundation of Innovation Academy for Green Manufacture Institute,Chinese Academy of Sciences(Grand No.IAGM2020C30).
文摘Current attempts in vaccine delivery systems concentrate on replicating the natural dissemination of live pathogens,but neglect that pathogens evolve to evade the immune system rather than to provoke it.In the case of enveloped RNA viruses,it is the natural dissemination of nucleocapsid protein(NP,core antigen)and surface antigen that delays NP exposure to immune surveillance.Here,we report a multi-layered aluminum hydroxide-stabilized emulsion(MASE)to dictate the delivery sequence of the antigens.In this manner,the receptor-binding domain(RBD,surface antigen)of the spike protein was trapped inside the nanocavity,while NP was absorbed on the outside of the droplets,enabling the burst release of NP before RBD.Compared with the natural packaging strategy,the inside-out strategy induced potent type I interferon-mediated innate immune responses and triggered an immune-potentiated environment in advance,which subsequently boosted CD40+DC activations and the engagement of the lymph nodes.In both H1N1 influenza and SARS-CoV-2 vaccines,rMASE significantly increased antigen-specific antibody secretion,memory T cell engagement,and Th1-biased immune response,which diminished viral loads after lethal challenge.By simply reversing the delivery sequence of the surface antigen and core antigen,the inside-out strategy may offer major implications for enhanced vaccinations against the enveloped RNA virus.
