With the blooming development of electronic technology,the use of electron conductive gel or ionic conductive gel in preparing flexible electronic devices is drawing more and more attention.Deep eutectic solvents are ...With the blooming development of electronic technology,the use of electron conductive gel or ionic conductive gel in preparing flexible electronic devices is drawing more and more attention.Deep eutectic solvents are excellent substitutes for ionic liquids because of their good biocompatibility,low cost,and easy preparation,except for good conductivity.In this work,we synthesized a reactive quaternary ammonium monomer(3-acrylamidopropyl)octadecyldimethyl ammonium bromide with a hydrophobic chain of 18 carbons via the quaternization of 1-bromooctadecane and N-dimethylaminopropyl acrylamide at first,then we mixed quaternary ammonium with choline chloride,acrylic acid and glycerol to obtain a hydrophobic deep eutectic solvent,and initialized polymerization in UV light of 365 nm to obtain the ionic conductive eutectogel based on polyacrylamide copolymer with long hydrophobic chain.The obtained eutectogel exibits good stretchability(1200%),Young's modulus(0.185 MPa),toughness(4.2 MJ/m^(3)),conductivity(0.315 S/m).The eutectogel also shows desireable moisture resistance with the maximum water absorption of 11.7 wt%after one week at 25℃ and 60% humidity,while the water absorption of eutectogel without hydrophobic long chains is 24.0 wt%.The introduction of long-chain hydrophobic groups not only improves the mechanical strength of the gels,but also significantly improves moisture resistance of the eutectogel.This work provides a simpler and more effective method for the preparation of ionic conductive eutectogels,which can further provide a reference for the applications of ionic conductive eutectogels in the field of flexible electronic devices.展开更多
The development of low-cost,abundant,and efficient non-metal catalysts has always been a research focus on photocatalytic hydrogen evolution reactions.Boron nitride nanosheet(BNNS),which is a promising non-metallic tw...The development of low-cost,abundant,and efficient non-metal catalysts has always been a research focus on photocatalytic hydrogen evolution reactions.Boron nitride nanosheet(BNNS),which is a promising non-metallic two-dimensional material,possesses remarkable properties.However,its inherently wide bandgap significantly limits their potential for visible-light-responsive catalysis,and conventional chemical methods struggle to overcome this limitation.In this study,we employed high-energy ionizing radiation to precisely regulate defect formation in BNNS at ambient temperature and pressure.The results showed that gamma-ray radiation markedly enhanced the efficiency of photocatalytic hydrogen production of the irradiated BNNS with increasing absorbed dose.The maximum hydrogen production rate of the samples reached 1033.7μmol/(g·h),which represents an increase of almost two orders of magnitude compared to commercial BNNS.The structural characterization also confirmed that the introduction of three-boron-center defects results in forming intermediate energy levels and improving the charge carrier separation efficiency of BNNS.This transformation converts BNNS from a wide bandgap semiconductor to a visible-light-responsive catalyst.This work not only provides a novel approach for the application of BNNS in visible-light photocatalysis,but also demonstrates the unique role of radiation technology in quantitatively regulating defects and improving catalytic activity.展开更多
Following publication of the original article[1],the authors reported an error in the last author’s name,it was mistakenly written as“Jun Den”.The correct author’s name“Jun Deng”has been updated in this Correction.
A series of stable waterborne polysiloxaneurethane （WPSUR） dispersions were prepared using amino-terminated polydimethylsiloxane （NS）, dimethylolpropionic acid （DMPA）, castor oil, polypropylene glycol and toluen...A series of stable waterborne polysiloxaneurethane （WPSUR） dispersions were prepared using amino-terminated polydimethylsiloxane （NS）, dimethylolpropionic acid （DMPA）, castor oil, polypropylene glycol and toluene diisocyanate. Meanwhile, NS with different molecular weights was synthesized and used as the soft co-segment. Effects of types and contents of soft co-segments as well as chain extenders on the thermal degradation and stability for WPSUR films were examined. Results reveal that WPSUR films exhibit excellent water resistance and mechanical properties as compared with pure polyurethane （PU） films, and the NS soft co-segment possesses a remarkable effect on the second stage （stage Ⅱ）, while the content of the hard segment is propitious to the initial stage （stage Ⅰ）. Moreover, the highest temperature of stage Ⅱ （T2m） for WPSUR films using NS as soft co-segment is 413℃, approximately being 30℃ higher than that of those typical PUs using HDA and APDMS as the chain extenders, respectively.展开更多
Acryloyl terminated Poly (ethyleneoxide)macromonomers (PEO-A) with different PEO chain lengths have been prepared by deactivation of PEO alkoxide with acryloyl chloride. A new kind of amphiphilic polystyrene-g-poly (e...Acryloyl terminated Poly (ethyleneoxide)macromonomers (PEO-A) with different PEO chain lengths have been prepared by deactivation of PEO alkoxide with acryloyl chloride. A new kind of amphiphilic polystyrene-g-poly (ethylene oxide)graft copolymer containing both microphase separated and PEO side chain structures has been synthesized from radical copolymerization of PEO-A macromonomer with styrene. After careful purification by a newly-developed method called 'selective dissolution', the well-defined structure of the purified copolymers was confirmed by IR, ~1H-NMR and GPC. Various experimental parameters controlling the copolymerization were studied in detail. The results indicated that the feed ratio of styrene to macromonomer(S/M) was the most important determining factor for the composition of the copolymers. A detailed 'comb- model' was proposed to describe the molecular structure of the graft copolymers. Finally, this amphiphilic graft copolymers may readily form microphase separated structures as clearly indicated by transmission electron microscopy.展开更多
The seminal report ofα-diimine palladium and nickel catalysts in 1995 represented a major breakthrough in the preparation of functionalized polyolefin materials.Owing to the high abundance and low cost of nickel,nick...The seminal report ofα-diimine palladium and nickel catalysts in 1995 represented a major breakthrough in the preparation of functionalized polyolefin materials.Owing to the high abundance and low cost of nickel,nickel-based catalysts have great application prospects in the industrialization process of olefin coordination polymerization.In this work,various N-aryl substituents with different electronic effects were synthesized and introduced intoα-diimine ligands.The aspreparedα-diimine nickel catalysts showed high polymerization activity(0.9×10^(7)–3.0×10^(7)g·mol^(−1)·h^(−1))in ethylene polymerization,generating polyethylene products with adjustable molecular weights(Mn values:7.4×10^(4)–146.9×10^(4)g·mol^(−1))and branching densities(31/1000 C–68/1000 C).The resulting polyethylene products showed excellent mechanical properties,with high tensile strength(up to 25.0 MPa)and high strain at break values(up to 3890%).The copolymerization of ethylene and polar monomers can also be achieved by these nicekel complexes,ultimately preparing functionalized polyolefins.展开更多
Fluorescent labels are widely used in the characterizations of DNA-based reaction network operations.We systematically studied the effects of commonly used fluorescent pairs on thermal stabilities of signal-substrate ...Fluorescent labels are widely used in the characterizations of DNA-based reaction network operations.We systematically studied the effects of commonly used fluorescent pairs on thermal stabilities of signal-substrate duplex and the strand displacement kinetics.It is demonstrated that the modifications of duplex with fluorescent pairs stabilize DNA duplex by up to 3.5℃,and the kinetics of DNA strand displacement circuit is also evidently slowed down.These results highlight the importance of fluorescent pairs towards the kinetic modulation in designing nucleic acid probes and complex DNA dynamic circuits.展开更多
High density polyethylene （HDPE）/polyethylene-block-poly（ethylene glycol） （PE-b-PEG） blend porous membranes were prepared via thermally induced phase separation （TIPS） process using diphenyl ether （DPE） as d...High density polyethylene （HDPE）/polyethylene-block-poly（ethylene glycol） （PE-b-PEG） blend porous membranes were prepared via thermally induced phase separation （TIPS） process using diphenyl ether （DPE） as diluent. The phase diagrams of HDPE/PE-b-PEG/DPE systems were determined by optical microscopy and differential scanning calorimetry （DSC）. By varying the content of PE-b-PEG, the effects of PE-b-PEG copolymer on morphology and crystalline structure of membranes were studied by scanning electron microscopy （SEM） and wide angle X-ray diffraction （WAXD）. The chemical compositions of whole membranes and surface layers were characterized by elementary analysis, Fourier transform infrared spectroscopy-attenuated total reflection （FTIR-ATR） and X-ray photoelectron spectroscopy （XPS）. Water contact angle, static protein adsorption and water flux experiments were used to evaluate the hydrophilicity, antifouling and water permeation properties of the membranes. It was found that the addition of PE-b-PEG increased the pore size of the obtained blend membranes. In the investigated range of PE-b-PEG content, the PEG blocks could not aggregate into obviously separated domains in membrane matrix. More importantly, PE-b-PEG could not only be retained stably in the membrane matrix during membrane formation, but also enrich at the membrane surface layer. Such stability and surface enrichment of PE-b-PEG endowed the blend membranes with improved hydrophilicity, protein absorption resistance and water permeation properties, which would be substantially beneficial to HDPE membranes for water treatment application.展开更多
Macrophage immunotherapy represents an emerging therapeutic approach aimed at modulating the immune response to alleviate disease symptoms.Nanomaterials(NMs)have been engineered to monitor macrophage metabolism,enabli...Macrophage immunotherapy represents an emerging therapeutic approach aimed at modulating the immune response to alleviate disease symptoms.Nanomaterials(NMs)have been engineered to monitor macrophage metabolism,enabling the evaluation of disease progression and the replication of intricate physiological signal patterns.They achieve this either directly or by delivering regulatory signals,thereby mapping phenotype to effector functions through metabolic repurposing to customize macrophage fate for therapy.However,a comprehensive summary regarding NM-mediated macrophage visualization and coordinated metabolic rewiring to maintain phenotypic equilibrium is currently lacking.This review aims to address this gap by outlining recent advancements in NM-based metabolic immunotherapy.We initially explore the relationship between metabolism,polarization,and disease,before delving into recent NM innovations that visualize macrophage activity to elucidate disease onset and fine-tune its fate through metabolic remodeling for macrophage-centered immunotherapy.Finally,we discuss the prospects and challenges of NM-mediated metabolic immunotherapy,aiming to accelerate clinical translation.We anticipate that this review will serve as a valuable reference for researchers seeking to leverage novel metabolic intervention-matched immunomodulators in macrophages or other fields of immune engineering.展开更多
Dielectric polymer nanocomposites are considered as one of the most promising candidates for high-power-density electrical energy storage applications.Inorganic nanofillers with high insulation property are frequently...Dielectric polymer nanocomposites are considered as one of the most promising candidates for high-power-density electrical energy storage applications.Inorganic nanofillers with high insulation property are frequently introduced into fluoropolymer to improve its breakdown strength and energy storage capability.Normally,inorganic nanofillers are thought to introducing traps into polymer matrix to suppress leakage current.However,how these nanofillers effect the leakage current is still unclear.Meanwhile,high dopant(>5 vol%)is prerequisite for distinctly improved energy storage performance,which severely deteriorates the processing and mechanical property of polymer nanocomposites,hence brings high technical complication and cost.Herein,boron nitride nanosheet(BNNS)layers are utilized for substantially improving the electrical energy storage capability of polyvinylidene fluoride(PVDF)nanocomposite.Results reveal that the high conduction band minimum of BNNS produces energy barrier at the interface of adjacent layers,preventing the electron in PVDF from passing through inorganic layers,leading to suppressed leakage current and superior breakdown strength.Accompanied by improved Young’s modulus(from 1.2 GPa of PVDF to 1.6 GPa of nanocomposite),significantly boosted discharged energy density(14.3 J cm^(-3)) and charge-discharge efficiency(75%)are realized in multilayered nanocomposites,which are 340 and 300% of PVDF(4.2 J cm^(-3),25%).More importantly,thus remarkably boosted energy storage performance is accomplished by marginal BNNS.This work offers a new paradigm for developing dielectric nanocomposites with advanced energy storage performance.展开更多
Rheological measurement has been a preferred approach to the characterization of the structure and phase behaviors for multi-component/multi-phase polymer systems, due to its sensitive response to the changes of struc...Rheological measurement has been a preferred approach to the characterization of the structure and phase behaviors for multi-component/multi-phase polymer systems, due to its sensitive response to the changes of structure for these heterogeneous polymers. In the present article, recent progresses in the studies on rheology for heterogeneous polymer systems including phase-separated polymeric blends and block copolymers are reviewed, mainly depending on the results by the authors＇ research group. By means of rheological measurements, not only some new fingerprints responsible for the evolution of morphology and structure concerning these polymer systems are obtained, also the corresponding results are significant for design and preparation of novel polymeric structural materials and functional materials.展开更多
H-type amphiphilic liquid crystalline block copolymers containing azobenzene were synthesized by atom transfer radical polymerization （ATRP）. Macroinitiators prepared by the esterification between poly（ethylene ox...H-type amphiphilic liquid crystalline block copolymers containing azobenzene were synthesized by atom transfer radical polymerization （ATRP）. Macroinitiators prepared by the esterification between poly（ethylene oxide） （PEG） and 2,2-dichloroacetyl chloride were utilized to initiate the polymerization of 6-[4-（4-ethoxyphenylazo）phenoxy]hexyl rnethacrylate （M6C）. The resulting macroinitiators and block copolymers were characterized by ^1H NMR, gel permeation chromatography （GPC）. Polarizing optical microscopy （POM） and differential scanning calorimetry （DSC） preliminarily revealed the liquid crystalline property of these block copolymers. This series of liquid crystalline block copolymers are promising in some areas, such as optical data storage, optical switch, and molecular devices.展开更多
A novel star-comb styrene/butadiene copolymer（SC-SBC） was synthesized by anionic polymerization and grafting reaction with epoxidized star liquid polybutadiene（ESPB） as coupling agent.The overall shape of the star...A novel star-comb styrene/butadiene copolymer（SC-SBC） was synthesized by anionic polymerization and grafting reaction with epoxidized star liquid polybutadiene（ESPB） as coupling agent.The overall shape of the star-comb macromolecules can be altered by changing the molecular weight and number of the side chain.The molecular parameters and mechanical properties of the SC-SBC resins were investigated.The notched izod impact strength of the SC-SBC resins are excellent and reach as high as to 239 J/m.展开更多
Planar polymer multi-model waveguides doped with Ag nano-particles and rhodamine B are fabricated and investigated by the spectroscopy analysis method as well as the M-line method. Experimental results shown that fluo...Planar polymer multi-model waveguides doped with Ag nano-particles and rhodamine B are fabricated and investigated by the spectroscopy analysis method as well as the M-line method. Experimental results shown that fluorescence enhancement occurs when excited by a wide band wavelength with Ag nano-particle concentration at a certain level. The maximum enhancement factor in our experiment is obtained to be about 3.8 when excited by 350 nm. Our study may have potential applications in polymers optical elements, such as polymer waveguide lasers and amplifiers.展开更多
A noncrystallizable semiaromatic polyamide copolymer（NSAP） was dissolved in molten caprolactam, and PA6/ NSAP blends were produced in-situ via the anionic ring-opening polymerization of caprolactam. The presence of ...A noncrystallizable semiaromatic polyamide copolymer（NSAP） was dissolved in molten caprolactam, and PA6/ NSAP blends were produced in-situ via the anionic ring-opening polymerization of caprolactam. The presence of a single loss tangent（tanS） peak measured by means of dynamic mechanical analysis（DMA） proves the miscibility between PA6 and NSAP in the blends. It was found that there existed drastic changes in the crystallographic form and crystallization kinetics for the in-situ blends, e.g. , when 20% NSAP was added, nearly all crystallites existed in the ,y form and the crystallization could hardly occur upon cooling even at a rate of 2.5 ℃/min. Moreover, cold crystallization appears during the subsequent heating, and its melting point is 40 ℃ lower than that of the virgin system. On the other hand, the size of the spherulites only decreases modestly. It is suggested that the introduction of irregular stiff segments originated from NSAP into PA6 macromolecule chain, which resulted from transamidation during the polymerization play a dominant role in the drastic change of crystallization kinetics and the resultant morphology of the in-situ blends.展开更多
The mechanical properties and dynamic mechanical properties of blends composed of Nylon 6 and poly （ butylenes terephthalate） （PBT）, with styrene/maleic anhydride（SMA） as compatibilizer, were studied. The observ...The mechanical properties and dynamic mechanical properties of blends composed of Nylon 6 and poly （ butylenes terephthalate） （PBT）, with styrene/maleic anhydride（SMA） as compatibilizer, were studied. The observation on the morphologies of the etched surfaces of the cryogenically fractured specimens via scanning electron microscopy（SEM） demonstrated that in the compatibilized Nylon 6/PBT blends, there exists a finer and more uniform dispersion induced by the in-situ interfacial chemical reactions during the preparation than that in the corresponding uncompatibilized blends. On the other hand, the overall mechanical properties of the compatibilized blends could be remarkably im- proved compared with those of the uncompatibilized ones. Moreover, increasing the amount of the compatibilizer SMA leads to a more efficient dispersion of the PBT phase in Nylon 6/PBT blends. Furthermore, there exists an optimum level of SMA added to achieve the maximum mechanical properties. As far as the mechanism of this reactive compatibilization is concerned, the enhanced interfacial adhesion is necessary to obtain improved dispersion, stable phase morphology, and better mechanical properties.展开更多
The electrochemical property of electrode materials greatly depends on their morphologies. This report introduces a novel and facile synthesis method for polyaniline (PANI) nanotubes from one-step synergistic polymeri...The electrochemical property of electrode materials greatly depends on their morphologies. This report introduces a novel and facile synthesis method for polyaniline (PANI) nanotubes from one-step synergistic polymerization of aniline and acrylic acid in an aqueous solution induced by the addition of ammonium persulfate (APS). The molar ratio of aniline to AA (X{ani/AA}) is found to have great in fluence on the morphology of the produced PANI. Hollow PANI nanotubes with an average inner diameter of 80 nm and outer diameter of 180 nm can be mainly produced when X{ani/AA} is not higher than 1. The electrochemical properties of the prepared PANI nanotubes have been investigated using a three-electrode system. The specific capacitance of PANI nanotubes can reach 436 F/g at a current density of 0.5 A/g in 1 mol/L H2SO4 solution. Furthermore, the specific capacitance of the PANI nanotube maintains 89.2% after 500 charging/discharging cycles at a current density of 0.5 A/g, indicating a good cycling stability.展开更多
Six preparation methods for polymeric organic-inorganic nanocomposites and their respective mechanisms and features are reviewed. The extraordinary properties of polymeric organic-inorganic nanocomposites are discusse...Six preparation methods for polymeric organic-inorganic nanocomposites and their respective mechanisms and features are reviewed. The extraordinary properties of polymeric organic-inorganic nanocomposites are discussed,and their potential applications are evaluated.展开更多
Critical association concentration (Ca) of ethylene-vinyl acetate copolymer (EVA) in selective solvent mixtures of 1,2-dichloroethane (DCE) (polar solvent) and cyclohexane (CYH) (non-polar solvent) was investigated. D...Critical association concentration (Ca) of ethylene-vinyl acetate copolymer (EVA) in selective solvent mixtures of 1,2-dichloroethane (DCE) (polar solvent) and cyclohexane (CYH) (non-polar solvent) was investigated. DCE is a good solvent for polyvinyl acetate (PVAc) and a poor solvent for paraffin, whereas CYH is a good solvent for the paraffin and a precipitant for PVAc. Viscosities of EVA in different compositions of the solvent mixture with and without additives were measured. Viscosity results were used to determine the C-A value of the systems. It is shown that C-A was markedly dependent on the composition of the solvent mixture and concentration and structure of the additive. Solvation and competition between hydrogen bonding and micellisation were suggested for qualitative description of the changing of C-A value observed.展开更多
Three new kinds of molecular networks are designed and predicted to exhibit negative Poisson ratios. Molecular mechanics calculations on these networks show that the magnitude of Poisson ratios depends on the relative...Three new kinds of molecular networks are designed and predicted to exhibit negative Poisson ratios. Molecular mechanics calculations on these networks show that the magnitude of Poisson ratios depends on the relative flexibility of beam and arm structures. Several new kinds of auxetic polymers, whose successful synthesis should be easier than that of the corresponding auxetic networks, are then proposed. It is found that the kabob-like polymers with auxegens lying vertically on the main chain can acquire auxeticity while those with auxegens lying horizontally on the main chain cannot. Besides, a half kabob-like or pseudo-ladder polymer with auxegens linked at the intersection of the beam and the arm does show auxeticity when adopting constrictive conformers. It is, however, worthwhile noting that the origins of auxeticity still await and strongly deserve further experimental and theoretical investigations.展开更多
基金This work was supported by the National Science and Technology Major Project of the Ministry of Science and Technology of China(No.2016ZX05016 and No.2016ZX05046).
文摘With the blooming development of electronic technology,the use of electron conductive gel or ionic conductive gel in preparing flexible electronic devices is drawing more and more attention.Deep eutectic solvents are excellent substitutes for ionic liquids because of their good biocompatibility,low cost,and easy preparation,except for good conductivity.In this work,we synthesized a reactive quaternary ammonium monomer(3-acrylamidopropyl)octadecyldimethyl ammonium bromide with a hydrophobic chain of 18 carbons via the quaternization of 1-bromooctadecane and N-dimethylaminopropyl acrylamide at first,then we mixed quaternary ammonium with choline chloride,acrylic acid and glycerol to obtain a hydrophobic deep eutectic solvent,and initialized polymerization in UV light of 365 nm to obtain the ionic conductive eutectogel based on polyacrylamide copolymer with long hydrophobic chain.The obtained eutectogel exibits good stretchability(1200%),Young's modulus(0.185 MPa),toughness(4.2 MJ/m^(3)),conductivity(0.315 S/m).The eutectogel also shows desireable moisture resistance with the maximum water absorption of 11.7 wt%after one week at 25℃ and 60% humidity,while the water absorption of eutectogel without hydrophobic long chains is 24.0 wt%.The introduction of long-chain hydrophobic groups not only improves the mechanical strength of the gels,but also significantly improves moisture resistance of the eutectogel.This work provides a simpler and more effective method for the preparation of ionic conductive eutectogels,which can further provide a reference for the applications of ionic conductive eutectogels in the field of flexible electronic devices.
文摘The development of low-cost,abundant,and efficient non-metal catalysts has always been a research focus on photocatalytic hydrogen evolution reactions.Boron nitride nanosheet(BNNS),which is a promising non-metallic two-dimensional material,possesses remarkable properties.However,its inherently wide bandgap significantly limits their potential for visible-light-responsive catalysis,and conventional chemical methods struggle to overcome this limitation.In this study,we employed high-energy ionizing radiation to precisely regulate defect formation in BNNS at ambient temperature and pressure.The results showed that gamma-ray radiation markedly enhanced the efficiency of photocatalytic hydrogen production of the irradiated BNNS with increasing absorbed dose.The maximum hydrogen production rate of the samples reached 1033.7μmol/(g·h),which represents an increase of almost two orders of magnitude compared to commercial BNNS.The structural characterization also confirmed that the introduction of three-boron-center defects results in forming intermediate energy levels and improving the charge carrier separation efficiency of BNNS.This transformation converts BNNS from a wide bandgap semiconductor to a visible-light-responsive catalyst.This work not only provides a novel approach for the application of BNNS in visible-light photocatalysis,but also demonstrates the unique role of radiation technology in quantitatively regulating defects and improving catalytic activity.
文摘Following publication of the original article[1],the authors reported an error in the last author’s name,it was mistakenly written as“Jun Den”.The correct author’s name“Jun Deng”has been updated in this Correction.
基金supported by the Science and Technology Department of Zhejiang Province(No.2006C11050)
文摘A series of stable waterborne polysiloxaneurethane （WPSUR） dispersions were prepared using amino-terminated polydimethylsiloxane （NS）, dimethylolpropionic acid （DMPA）, castor oil, polypropylene glycol and toluene diisocyanate. Meanwhile, NS with different molecular weights was synthesized and used as the soft co-segment. Effects of types and contents of soft co-segments as well as chain extenders on the thermal degradation and stability for WPSUR films were examined. Results reveal that WPSUR films exhibit excellent water resistance and mechanical properties as compared with pure polyurethane （PU） films, and the NS soft co-segment possesses a remarkable effect on the second stage （stage Ⅱ）, while the content of the hard segment is propitious to the initial stage （stage Ⅰ）. Moreover, the highest temperature of stage Ⅱ （T2m） for WPSUR films using NS as soft co-segment is 413℃, approximately being 30℃ higher than that of those typical PUs using HDA and APDMS as the chain extenders, respectively.
基金Supported by the National Natural Science Foundation of China and the State Education Committee of China
文摘Acryloyl terminated Poly (ethyleneoxide)macromonomers (PEO-A) with different PEO chain lengths have been prepared by deactivation of PEO alkoxide with acryloyl chloride. A new kind of amphiphilic polystyrene-g-poly (ethylene oxide)graft copolymer containing both microphase separated and PEO side chain structures has been synthesized from radical copolymerization of PEO-A macromonomer with styrene. After careful purification by a newly-developed method called 'selective dissolution', the well-defined structure of the purified copolymers was confirmed by IR, ~1H-NMR and GPC. Various experimental parameters controlling the copolymerization were studied in detail. The results indicated that the feed ratio of styrene to macromonomer(S/M) was the most important determining factor for the composition of the copolymers. A detailed 'comb- model' was proposed to describe the molecular structure of the graft copolymers. Finally, this amphiphilic graft copolymers may readily form microphase separated structures as clearly indicated by transmission electron microscopy.
基金supported by the National Key R&D Program of China(2021YFA1501700)Fundamental Research Funds for the Central Universities(WK9990000142).
文摘The seminal report ofα-diimine palladium and nickel catalysts in 1995 represented a major breakthrough in the preparation of functionalized polyolefin materials.Owing to the high abundance and low cost of nickel,nickel-based catalysts have great application prospects in the industrialization process of olefin coordination polymerization.In this work,various N-aryl substituents with different electronic effects were synthesized and introduced intoα-diimine ligands.The aspreparedα-diimine nickel catalysts showed high polymerization activity(0.9×10^(7)–3.0×10^(7)g·mol^(−1)·h^(−1))in ethylene polymerization,generating polyethylene products with adjustable molecular weights(Mn values:7.4×10^(4)–146.9×10^(4)g·mol^(−1))and branching densities(31/1000 C–68/1000 C).The resulting polyethylene products showed excellent mechanical properties,with high tensile strength(up to 25.0 MPa)and high strain at break values(up to 3890%).The copolymerization of ethylene and polar monomers can also be achieved by these nicekel complexes,ultimately preparing functionalized polyolefins.
基金This work was supported by the National Natural Science Foundation of China(No.22073090 No.21991132,No.52021002)the National Key R&D Program of China(No.2020YFA0710703)the Funds of Youth Innovation Promotion Association and the Fun damental Research Funds for the Central Universities.
文摘Fluorescent labels are widely used in the characterizations of DNA-based reaction network operations.We systematically studied the effects of commonly used fluorescent pairs on thermal stabilities of signal-substrate duplex and the strand displacement kinetics.It is demonstrated that the modifications of duplex with fluorescent pairs stabilize DNA duplex by up to 3.5℃,and the kinetics of DNA strand displacement circuit is also evidently slowed down.These results highlight the importance of fluorescent pairs towards the kinetic modulation in designing nucleic acid probes and complex DNA dynamic circuits.
基金supported by the 863 program(No.2006AA03Z233)973 program(No.2009CB623402) of China
文摘High density polyethylene （HDPE）/polyethylene-block-poly（ethylene glycol） （PE-b-PEG） blend porous membranes were prepared via thermally induced phase separation （TIPS） process using diphenyl ether （DPE） as diluent. The phase diagrams of HDPE/PE-b-PEG/DPE systems were determined by optical microscopy and differential scanning calorimetry （DSC）. By varying the content of PE-b-PEG, the effects of PE-b-PEG copolymer on morphology and crystalline structure of membranes were studied by scanning electron microscopy （SEM） and wide angle X-ray diffraction （WAXD）. The chemical compositions of whole membranes and surface layers were characterized by elementary analysis, Fourier transform infrared spectroscopy-attenuated total reflection （FTIR-ATR） and X-ray photoelectron spectroscopy （XPS）. Water contact angle, static protein adsorption and water flux experiments were used to evaluate the hydrophilicity, antifouling and water permeation properties of the membranes. It was found that the addition of PE-b-PEG increased the pore size of the obtained blend membranes. In the investigated range of PE-b-PEG content, the PEG blocks could not aggregate into obviously separated domains in membrane matrix. More importantly, PE-b-PEG could not only be retained stably in the membrane matrix during membrane formation, but also enrich at the membrane surface layer. Such stability and surface enrichment of PE-b-PEG endowed the blend membranes with improved hydrophilicity, protein absorption resistance and water permeation properties, which would be substantially beneficial to HDPE membranes for water treatment application.
基金financially supported by the National Natural Science Foundation of China(Nos.92168106 and 82222039).
文摘Macrophage immunotherapy represents an emerging therapeutic approach aimed at modulating the immune response to alleviate disease symptoms.Nanomaterials(NMs)have been engineered to monitor macrophage metabolism,enabling the evaluation of disease progression and the replication of intricate physiological signal patterns.They achieve this either directly or by delivering regulatory signals,thereby mapping phenotype to effector functions through metabolic repurposing to customize macrophage fate for therapy.However,a comprehensive summary regarding NM-mediated macrophage visualization and coordinated metabolic rewiring to maintain phenotypic equilibrium is currently lacking.This review aims to address this gap by outlining recent advancements in NM-based metabolic immunotherapy.We initially explore the relationship between metabolism,polarization,and disease,before delving into recent NM innovations that visualize macrophage activity to elucidate disease onset and fine-tune its fate through metabolic remodeling for macrophage-centered immunotherapy.Finally,we discuss the prospects and challenges of NM-mediated metabolic immunotherapy,aiming to accelerate clinical translation.We anticipate that this review will serve as a valuable reference for researchers seeking to leverage novel metabolic intervention-matched immunomodulators in macrophages or other fields of immune engineering.
基金supported by China Postdoctoral Science Foundation(2021M690103)National Natural Science Foundation of China(52003153,51877132,and 52002300)+2 种基金Program of Shanghai Academic Research Leader(21XD1401600)State Key Laboratory of Electrical Insulation and Power Equipment(EIPE20203,EIPE21206)the Major Research Plan of National Natural Science Foundation of China(92066103)。
文摘Dielectric polymer nanocomposites are considered as one of the most promising candidates for high-power-density electrical energy storage applications.Inorganic nanofillers with high insulation property are frequently introduced into fluoropolymer to improve its breakdown strength and energy storage capability.Normally,inorganic nanofillers are thought to introducing traps into polymer matrix to suppress leakage current.However,how these nanofillers effect the leakage current is still unclear.Meanwhile,high dopant(>5 vol%)is prerequisite for distinctly improved energy storage performance,which severely deteriorates the processing and mechanical property of polymer nanocomposites,hence brings high technical complication and cost.Herein,boron nitride nanosheet(BNNS)layers are utilized for substantially improving the electrical energy storage capability of polyvinylidene fluoride(PVDF)nanocomposite.Results reveal that the high conduction band minimum of BNNS produces energy barrier at the interface of adjacent layers,preventing the electron in PVDF from passing through inorganic layers,leading to suppressed leakage current and superior breakdown strength.Accompanied by improved Young’s modulus(from 1.2 GPa of PVDF to 1.6 GPa of nanocomposite),significantly boosted discharged energy density(14.3 J cm^(-3)) and charge-discharge efficiency(75%)are realized in multilayered nanocomposites,which are 340 and 300% of PVDF(4.2 J cm^(-3),25%).More importantly,thus remarkably boosted energy storage performance is accomplished by marginal BNNS.This work offers a new paradigm for developing dielectric nanocomposites with advanced energy storage performance.
基金This work was supported by the Special Funds for Major Stale Basic Research Projects (No. 2005CB623802) National Natural Science Foundation of China (No. 50373037).
文摘Rheological measurement has been a preferred approach to the characterization of the structure and phase behaviors for multi-component/multi-phase polymer systems, due to its sensitive response to the changes of structure for these heterogeneous polymers. In the present article, recent progresses in the studies on rheology for heterogeneous polymer systems including phase-separated polymeric blends and block copolymers are reviewed, mainly depending on the results by the authors＇ research group. By means of rheological measurements, not only some new fingerprints responsible for the evolution of morphology and structure concerning these polymer systems are obtained, also the corresponding results are significant for design and preparation of novel polymeric structural materials and functional materials.
基金financial support from the National Natural Science Foundation of China(No.20134020)the Science Research Fund of the Chinese Ministry of Education(No.104005)the Science Research Fund of Shandong Provincial Education Department of China(No.105D11).
文摘H-type amphiphilic liquid crystalline block copolymers containing azobenzene were synthesized by atom transfer radical polymerization （ATRP）. Macroinitiators prepared by the esterification between poly（ethylene oxide） （PEG） and 2,2-dichloroacetyl chloride were utilized to initiate the polymerization of 6-[4-（4-ethoxyphenylazo）phenoxy]hexyl rnethacrylate （M6C）. The resulting macroinitiators and block copolymers were characterized by ^1H NMR, gel permeation chromatography （GPC）. Polarizing optical microscopy （POM） and differential scanning calorimetry （DSC） preliminarily revealed the liquid crystalline property of these block copolymers. This series of liquid crystalline block copolymers are promising in some areas, such as optical data storage, optical switch, and molecular devices.
基金financially supported by the National High Technology Research and Development Program of China(No.2007AA03Z532)the National Natural Science Foundation of China(No.20774015)the China National Petroleum Corporation Innovation Fund(No.07E1034)
文摘A novel star-comb styrene/butadiene copolymer（SC-SBC） was synthesized by anionic polymerization and grafting reaction with epoxidized star liquid polybutadiene（ESPB） as coupling agent.The overall shape of the star-comb macromolecules can be altered by changing the molecular weight and number of the side chain.The molecular parameters and mechanical properties of the SC-SBC resins were investigated.The notched izod impact strength of the SC-SBC resins are excellent and reach as high as to 239 J/m.
基金Supported by the National Natural Science Foundation of China under Grant No 10474093, the National Basic Research Programme of China under Grant No 2006CB302900, and the Special Funds for Major State Basic Research Programme of China under Grant No 2005CCA04200.
文摘Planar polymer multi-model waveguides doped with Ag nano-particles and rhodamine B are fabricated and investigated by the spectroscopy analysis method as well as the M-line method. Experimental results shown that fluorescence enhancement occurs when excited by a wide band wavelength with Ag nano-particle concentration at a certain level. The maximum enhancement factor in our experiment is obtained to be about 3.8 when excited by 350 nm. Our study may have potential applications in polymers optical elements, such as polymer waveguide lasers and amplifiers.
基金Supported by the National Natural Science Foundation of China(No50373037)
文摘A noncrystallizable semiaromatic polyamide copolymer（NSAP） was dissolved in molten caprolactam, and PA6/ NSAP blends were produced in-situ via the anionic ring-opening polymerization of caprolactam. The presence of a single loss tangent（tanS） peak measured by means of dynamic mechanical analysis（DMA） proves the miscibility between PA6 and NSAP in the blends. It was found that there existed drastic changes in the crystallographic form and crystallization kinetics for the in-situ blends, e.g. , when 20% NSAP was added, nearly all crystallites existed in the ,y form and the crystallization could hardly occur upon cooling even at a rate of 2.5 ℃/min. Moreover, cold crystallization appears during the subsequent heating, and its melting point is 40 ℃ lower than that of the virgin system. On the other hand, the size of the spherulites only decreases modestly. It is suggested that the introduction of irregular stiff segments originated from NSAP into PA6 macromolecule chain, which resulted from transamidation during the polymerization play a dominant role in the drastic change of crystallization kinetics and the resultant morphology of the in-situ blends.
基金Supported by the Natural Science Funds of Guizhou Province,China(No.GY-2005-3036)the National Basic Research Pro-gram of China(No.2005CB623802).
文摘The mechanical properties and dynamic mechanical properties of blends composed of Nylon 6 and poly （ butylenes terephthalate） （PBT）, with styrene/maleic anhydride（SMA） as compatibilizer, were studied. The observation on the morphologies of the etched surfaces of the cryogenically fractured specimens via scanning electron microscopy（SEM） demonstrated that in the compatibilized Nylon 6/PBT blends, there exists a finer and more uniform dispersion induced by the in-situ interfacial chemical reactions during the preparation than that in the corresponding uncompatibilized blends. On the other hand, the overall mechanical properties of the compatibilized blends could be remarkably im- proved compared with those of the uncompatibilized ones. Moreover, increasing the amount of the compatibilizer SMA leads to a more efficient dispersion of the PBT phase in Nylon 6/PBT blends. Furthermore, there exists an optimum level of SMA added to achieve the maximum mechanical properties. As far as the mechanism of this reactive compatibilization is concerned, the enhanced interfacial adhesion is necessary to obtain improved dispersion, stable phase morphology, and better mechanical properties.
基金supported by the National Natural Science Foundation of China (No.51473152, No.51573174, and No.51773189)the Fundamental Research Funds for the Central Universities (No.WK3450000001 and No.WK3450000004).
文摘The electrochemical property of electrode materials greatly depends on their morphologies. This report introduces a novel and facile synthesis method for polyaniline (PANI) nanotubes from one-step synergistic polymerization of aniline and acrylic acid in an aqueous solution induced by the addition of ammonium persulfate (APS). The molar ratio of aniline to AA (X{ani/AA}) is found to have great in fluence on the morphology of the produced PANI. Hollow PANI nanotubes with an average inner diameter of 80 nm and outer diameter of 180 nm can be mainly produced when X{ani/AA} is not higher than 1. The electrochemical properties of the prepared PANI nanotubes have been investigated using a three-electrode system. The specific capacitance of PANI nanotubes can reach 436 F/g at a current density of 0.5 A/g in 1 mol/L H2SO4 solution. Furthermore, the specific capacitance of the PANI nanotube maintains 89.2% after 500 charging/discharging cycles at a current density of 0.5 A/g, indicating a good cycling stability.
基金Supported by Phosphor Plan of Science Technology of Young Scientists of Shanghai(No.00QE14047).
文摘Six preparation methods for polymeric organic-inorganic nanocomposites and their respective mechanisms and features are reviewed. The extraordinary properties of polymeric organic-inorganic nanocomposites are discussed,and their potential applications are evaluated.
基金The project was supported by National Natural Science Foundation of China(No.29774020).
文摘Critical association concentration (Ca) of ethylene-vinyl acetate copolymer (EVA) in selective solvent mixtures of 1,2-dichloroethane (DCE) (polar solvent) and cyclohexane (CYH) (non-polar solvent) was investigated. DCE is a good solvent for polyvinyl acetate (PVAc) and a poor solvent for paraffin, whereas CYH is a good solvent for the paraffin and a precipitant for PVAc. Viscosities of EVA in different compositions of the solvent mixture with and without additives were measured. Viscosity results were used to determine the C-A value of the systems. It is shown that C-A was markedly dependent on the composition of the solvent mixture and concentration and structure of the additive. Solvation and competition between hydrogen bonding and micellisation were suggested for qualitative description of the changing of C-A value observed.
基金The financial support of the NSFC (20274004) and P&G is gratefully acknowledged.
文摘Three new kinds of molecular networks are designed and predicted to exhibit negative Poisson ratios. Molecular mechanics calculations on these networks show that the magnitude of Poisson ratios depends on the relative flexibility of beam and arm structures. Several new kinds of auxetic polymers, whose successful synthesis should be easier than that of the corresponding auxetic networks, are then proposed. It is found that the kabob-like polymers with auxegens lying vertically on the main chain can acquire auxeticity while those with auxegens lying horizontally on the main chain cannot. Besides, a half kabob-like or pseudo-ladder polymer with auxegens linked at the intersection of the beam and the arm does show auxeticity when adopting constrictive conformers. It is, however, worthwhile noting that the origins of auxeticity still await and strongly deserve further experimental and theoretical investigations.
